TWI249545B - Method of post-polymerization injection in condensation polymer production - Google Patents

Abstract

The invention is a novel method for the late introduction of additives into a process for making condensation polymers. The method employs a reactive carrier that functions as a delivery vehicle for one or more additives. The reactive carrier reacts with the condensation polymers, thereby binding the reactive carrier in the polymer resin and preventing the emergence of the reactive carrier from the polymer resin during subsequent thermal processing.

Description

1249545 A7 B7 V. INSTRUCTIONS INSTRUCTIONS (丨) RELATED APPLICATIONS This application is based on US Serial No. 10/017, 612, filed on Dec. The continuation of the method of Post-Polymerization Injection in Condensation Polymer Production), the first patent of which is filed on August 17, 2001, in the application Serial No. 09/932,150, in the process of polyethylene terephthalate. After the continuation of the "Methods of Post-Polymerization Extruder Injection In Polyethylene Terephthalate Production", the first patent itself is the US application number 09/73 8,150 filed on December 15, 2000. Part of the "Methods of Post-Polymerization Injection in Continuous Polyethylene Terephthalate Production" continues. The present application is also related to U.S. Application Serial No. 10/017,400, filed on Dec. 14, 2001, to the "Methods of Post-Polymerization Extruder Injection in Condensation Polymer Production". Related. The applications in each of these applications are hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in its entirety herein in its entirety Scope of the Invention The present invention relates to the manufacture of condensation polymers. More specifically, the present invention relates to the late introduction of an additive to a condensation polymer via a reactive carrier. Background of the Invention -_- 4 -_ This paper scale applies to China National Standard (CNS) Α4 specification (21〇χ 297 mm) 1249545 A7 — ___ — ____ B7 V. INSTRUCTIONS (2) Polyester fibers and films are integral to many consumer products manufactured worldwide because of their strength, heat resistance, and chemical resistance. Most of the commercial polyester-based polyethylene terephthalate (PET) polyesters used in polyester fibers and films. Since polyethylene terephthalate forms a light and shatterproof product, another common use of polyethylene terephthalate is as a resin for containers, especially for beverage bottles. Prior to 1965, the only viable process for making polyethylene terephthalate polyesters was to use dimethyl terephthalate (DMT). In this technique, dimethyl terephthalate and ethylene glycol are reacted in a catalytic transesterification reaction to form bis(2-hydroxyethyl)terephthalate monomers and oligomers, and continuously shifted. Removal of methanol by-products. Then, these bis(2-hydroxyethyl)terephthalic acid phenolic monomers and oligomers are polymerized by condensation polymerization to produce a polyethylene terephthalate polymer. It is now easier to obtain a more pure form of terephthalic acid (TA). Therefore, terephthalic acid, if not preferred, has also become an acceptable substitute for dimethyl terephthalate as a raw material for the production of polyethylene terephthalate. In this alternative technique, terephthalic acid and ethylene glycol are reacted in a generally uncatalyzed esterification reaction to produce low molecular weight monomers and oligomers, as well as continuously removed water by-products. As with the dimethyl terephthalate technology, the monomers and oligomers are then polymerized by condensation polymerization to form a polyethylene terephthalate polyester. The resulting polyethylene terephthalate polymer is substantially the same as the polyethylene terephthalate polymer formed from dimethyl terephthalate, although it has some different terminal groups. Poly(ethylene terephthalate) polyester can be produced in a batch process, where the paper gg standard (CNS) A4 specification is applied to the paper scale ((10)xNonggongai) - 1249545 A7 B7 V. Invention description (3 The product of s intended to be exchanged or self-reacted, and then transferred to a second vessel for polymerization. The second vessel is generally stirred and the polymerization is continued until the power used by the agitator reaches the indicated concentration. The lining has reached the desired intrinsic viscosity '&<>> to achieve the desired molecular value. However, it is commercially more (4) to carry out the self-conversion or g-exchange reaction, and then carry out the polymerization as a continuous process. The continuous manufacture of polyethylene terephthalate produces a large amount of discharge, so it is well-known in large-scale manufacturing equipment. When the polymerization process is completed, the polymer (4) which is typically formed is extruded and pelletized. It can be conveniently stored and transported before being converted into a specific object (for example, a filament, a film, or a bottle), and the latter step is referred to herein as "polyester processing." In batch and continuous processes, Usually used The active catalyst can increase the concentration of the polymer, thereby increasing the yield of the polyethylene terephthalate polyester (IV). The high-activity catalyst used for the polymerization of polyethylene terephthalate can be Alkaline, acidic, or neutral, and it is usually a metal catalyst. /吏 is used for the tradition of self-terephthalic acid and terephthalic acid dimethyl sulfonate to form polyethylene terephthalate. The polymerization catalyst mainly contains ruthenium, which is most often ruthenium trioxide (Sb2〇3). The polymerization catalyst like ruthenium trioxide can increase the production rate, but it will eventually start to catalyze or promote polyethylene terephthalate. Degradation of the polymer. The degradation of this polymer leads to the formation of acetaldehyde, the discoloration of poly(ethylene diacetate), and the discoloration of the polymer (for example, yellowing), and the availability of polymer molecular catalysts. Can significantly increase the amount of discharge

1249545 A7 B7 V. INSTRUCTIONS (4) The use of properties creates the relative need for better stability of the resulting polyester. U.S. Patent No. 5,008,230, "Catalyst for Preparing High Clarity (Colorless Polyethylene Terephthalate)" is an example of such an improved catalyst. In order to reduce the degradation and discoloration of the polyethylene terephthalate polyester, the stabilized compound is used to suppress ("cool") the catalyst, thereby reducing its effectiveness. The most commonly used stabilizers include phosphorus, which is typically in the form of phosphates and phosphites. Phosphate-containing stabilizers are first used in batch processes to prevent degradation and discoloration of polyethylene terephthalate polyesters. Although the addition of a stabilizer to a polymer melt system in a batch reactor is a relatively simple procedure, the addition of a stabilizer to the continuous manufacture of polyethylene terephthalate will create a number of problems. For example, although the early addition of a stabilizer prevents discoloration and degradation of the polyester, it also results in a reduced manufacturing throughput (even if the condensation polymerization rate is reduced). In addition, such stabilizers are typically dissolved in ethylene glycol and their addition will further slow down the polymerization process. Therefore, the early addition of a stabilizer in the polymerization process requires an undesired choice between the amount of material produced and the thermal stability of the polymer. As used herein, "thermal stability" means low acetaldehyde production rate, low discoloration, and retention of molecular weight after subsequent heat treatment or other processing. Subsequent addition of the stabilizer (for example, during the polymer processing process) does not provide sufficient opportunity for the stabilizer to fully blend with the polymer. Therefore, the stabilizer cannot prevent the degradation and discoloration of the poly S. In addition, the addition of stabilizers during polymer processing is inconvenient and does not provide an economical scale. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1249545 A7 B7 V. Invention description (5) US Patent No. 5,376,702, "Method and device for direct and continuous modification of polymer melt ( Process and Apparatus for the Direct and Continuous Modification of Polymer Melts) discloses the separation of a polymer melt stream into a stream that is unmodified and accepts additives. In particular, the side stream takes a portion of the side stream to an extruder where an additive is introduced. However, this technique is not only complicated but also expensive, requiring screw extruders and solution tubes for processing additives. Therefore, such an arrangement is inconvenient and even impractical, wherein the total additive concentration is low (e.g., less than 1 weight percent). U.S. Patent No. 5,898,058, "Method of Post-Polymerization Stabilization of High Activity Catalysts in Continuous Polyethylene Terephthalate Production" The specific problem associated with the addition of stabilizers in the later stages reveals a method for stabilizing high activity polymeric catalysts in a continuous polyethylene terephthalate process. This patent is hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in its entirety herein in its entirety In particular, U.S. Patent No. 5,898,058 discloses the addition of a stabilizer, preferably at the end of or after the polymerization and prior to polymer processing, which comprises phosphorus. This deactivates the polymerization catalyst and increases the amount of polyester discharged without adversely affecting the thermal stability of the polyethylene terephthalate polyester. Although it is a significant improvement over the prior art, U.S. Patent No. 5,898,058 teaches the use of a stabilizer without the use of a carrier. Therefore, the addition of a solid to a polymer requires expensive use of a squeegee. -8- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Α7 Β7 1249545 V. Invention description (γ \ 6 US Patent Application Serial No. 09/738,150, "Continuous Poly Terephthalic Acid </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; U.S. Patent Application Serial No. 9/738,150 discloses a process for the late introduction of an additive into the process of polyethylene terephthalate. The additive is a condensation polymerization of a polyethylene terephthalate polymer. Introduced in and after, and preferably introduced thereafter. In particular, the method uses a carrier which is not only a transporting agent for one or more additives, but also reacts with polyethylene terephthalate, thus the carrier Incorporating in a polyethylene terephthalate resin. In addition, U.S. Patent Application Serial No. 9/738, filed on Jan. No. No. No. No. No. No. No. No. No. No. No. No. No. 9/738, (U.S. Application Serial No. 09/932,150, "Injection Process for Polymerization Extrusion Machines in the Process of Polyethylene Terephthalate Ethylene Glycol", which is a continuation of the U.S. Application Serial No. 09/738,150, which discloses The method of introducing additives in the late stage of the extruder in the process of polyethylene terephthalate. The technology of US Application No. 09/738,150 can be effectively used in the joint application and the commonly assigned US application serial number 09/ 738,619 "Resinester Resins Having Reduced Frictional Properties and Methods for

Making the Same), this patent is also filed on Dec. 15, 2000, the entire disclosure of which is incorporated herein by reference. The particular preferred embodiment of U.S. Application Serial No. 09/738,619 also utilizes a simplified additive delivery system that does not require the use of an extruder. -9 - This paper size applies to China National Standard (CNS) A4 specification (210X297 public)

1249545 A7 B7 5 invention description (The method of Wu Guo Patent Application No. 9/738,150 can be applied to the general manufacture of condensation polymers. In fact, there is a need to ensure that the introduction of additives in the later stages of the condensate process can produce additives. And a post-polymerization injection technique of a condensation polymer in which the carrier is an integral part of the resin. Summary of the Invention Accordingly, it is an object of the present invention to provide a reaction carrier which will be substantially after completion of the melt phase condensation polymerization. A method of adding an additive to a condensation polymer. A further object of the present invention is to provide an additive to a condensation polymer via a reactive carrier to reduce polymer transition time and to eliminate turbulence caused by changing polymer formulations. A further object of the present invention is to provide a process for introducing such an additive into a condensation polymer in a manner which reduces degradation or volatilization of the additive. A further object of the present invention is to provide a simplified additive delivery system, Where the reactive carrier is a pumpable liquid at or near room temperature or A further object of the present invention is to provide a simplified additive delivery system that does not require the use of an extruder to deliver the additive. A further object of the present invention is to provide an improvement as disclosed in U.S. Patent No. 5,898,058 A continuous process for the condensation polymer of a stabilizer addition technique, such as a high quality polyethylene terephthalate polyester. The foregoing and other objects and advantages of the present invention, and the manner in which it is achieved, are further described in detail below. And its drawings. Schematic description: -10 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm)

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1249545 A7 B7 V. DESCRIPTION OF THE INVENTION (Fig. 1 illustrates the theoretical loss (measured by number average degree of polymerization) of a molecular weight of a condensation polymer having an initial polymerization degree of about 1 Å into a concentration of a reactive carrier at a different molecular weight. Figure 2. Figure 2 illustrates the theoretical loss (measured by number average degree of polymerization) of the molecular weight of a condensation polymer having an initial degree of polymerization of about 70 as a function of the concentration of the reactive carrier at different molecular weights. The theoretical loss of the intrinsic viscosity of polyethylene terephthalate having an intrinsic viscosity of 0.63 dl/g (dl/g) is a function of the concentration of the reactive carrier at different molecular weights. Figure 4 illustrates having 0.45 The theoretical loss of the intrinsic viscosity of polyethylene terephthalate having an intrinsic viscosity of dl/gram is a function of the concentration of the reactive carrier at different molecular weights. DETAILED DESCRIPTION The present invention is a late introduction of an additive into a condensation polymer. A new method in the process. Additives are introduced in the condensation polymerization and are introduced later. In particular, this method is used not only as one or more additions. a transport vehicle, and a reactive carrier that also reacts with the condensation polymer, thereby incorporating the reactive support into the polymer resin, which prevents subsequent processing of the reactive support, such as solid state polymerization, drying operations, spinning In the operation, film extrusion, and injection molding operations, the self-condensing polymer is removed. This also improves the dispersion of the additive in the condensation polymer and reduces the tendency of the carrier to deposit in the polymer processing equipment in solid hydration. Thus, in the preferred embodiment, the invention includes the polymerization of oligomeric precursors via condensation-polymerization of the melt-phase, resulting in a shrinking functionality.

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1249545 A7 ---------B7 V. INSTRUCTIONS (9) The saliva mouth is then passed through a reactive carrier with a molecular weight of less than about 1 gram per mole. Introduced into the condensation polymer. In another preferred embodiment, the invention comprises the action of a condensed polycondensation precursor through a fused-condensation phase to form a condensation polymer having a carbonyl functionality and an average degree of polymerization of at least about 70. After the condensation polymer reaches the water level of the crucible, one or more additives are introduced into the condensation polymer via a reactive carrier having a knife of less than about 1 Torr, a gram/mole. Thereafter the condensation is completed. This melt-phase condensation polymerization of the polymer. When the S additive is introduced during the condensation polymerization, the average degree of polymerization of the target is preferably: /, · 80, preferably at least about 9 Torr and at least about 1 (9) is optimal. At an average degree of polymerization of at least about 70, the condensed polymer develops chain entanglements that produce useful properties such as melt strength, impact resistance, and modulus. Those familiar with the technique of the grommets recognize that the additive is added to the additive at a later stage. The condensation polymerization 13⁄4 &amp; or occurs in the condensation polymerization stage (i.e., wherein the average degree of polymerization of the condensation polymer is at least about 7 Å), and the specific embodiments of the invention disclosed herein are applicable. As used herein, the term "carbonyl functionality" refers to carbon-based sufficient for effective response unit site - oxygen double bond. A condensation polymer having a carbonyl functionality is typically characterized by the presence of a carbonyl functional group having at least one adjacent hetero atom (e.g., an oxygen atom, a nitrogen atom, or a sulfur atom) as a chain within the polymer chain ( That is). Thus, "carbonyl functional" is meant to include various functional groups including, but not limited to, esters, decylamines, quinones, carbonates, and urethanes. Suitable condensation polymers according to the invention include, but are not limited to, poly-12-^ paper scales applicable to the Chinese National Standard (CNS) A4 specification (21〇χ297 mm) - 1249545 A7 B7 V. Description of invention (1 ( )) Esters, polyurethanes, polycarbonates, polyamines, and polyimines. Polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate are preferred. As is apparent to those skilled in the art, the oligomeric precursor of the condensation polymer can be formed by reacting the first polyfunctional component with the second polyfunctional component. For example, an oligomeric precursor of a polycarbonate can be formed by reacting a diol with a derivative of carbonic acid, and an oligomeric precursor of a polyurethane can be formed by reacting a diisocyanate with a glycol. An oligomeric precursor which forms a polyamine by reacting a dibasic acid with a diamine, and an oligomeric precursor which can form a polyimine by reacting a dianhydride with a diamine. See, for example, Odian, Principles of Polymerization, (2nd ed. 1981) 人士 Those familiar with polymer technology are fully aware of these types of reactions and will not be discussed further herein. It is clear to those skilled in the art that a particular monomer having polyfunctionality can self-polymerize to produce a condensation polymer. For example, the amino acid and the nylon salt can each be self-polymerized to a polyamine, and the hydroxy acid (e.g., lactic acid) can be self-polymerized into a polyester (e.g., polylactic acid). The polyester is a preferred condensation polymer, and therefore the invention is described herein with particular reference to the process of introducing an additive into polyethylene terephthalate. To this end, an oligomeric precursor of the polyester can be formed by reacting a dibasic acid with a glycol or by reacting a dibasic ester with a glycol. The glycol may be aliphatic or aromatic. Those skilled in the art of polymerizing it will be apparent that the description of the invention is not only directed to the introduction of additives to polyethylene terephthalate, but also to the application of the Chinese National Standard (CNS) A4 specification for the addition of -13 - this paper size ( 210X 297 mm) Binding

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The agent is incorporated into any condensed polymer having carbonyl functionality along the polymer chain thereof. It is contemplated that the exemplification of the present invention using a preferred condensation polymer (i.e., polyethylene terephthalate) will allow anyone skilled in the art of the polymer to practice any condensation polymer having carbonyl functionality without undue experimentation. Invention. To this end, those skilled in the art of polymer art know that many types of condensation polymers and copolymers can be synthesized without departing from the scope and spirit of the invention. The present invention comprises reacting a terephthalate component with a glycol component to form a polyethylene terephthalate precursor, such as bis(2-hydroxyethyl)terephthalate. These oligomeric precursors are then polymerized by melt phase condensation polymerization to form a polymer of polyethylene terephthalate. In the condensation polymerization process which is usually promoted by a catalyst, ethylene glycol is continuously removed to produce a favorable reaction kinetic energy. Thereafter, one or more additives are introduced into the polyethylene terephthalate polymer via a reactive carrier (i.e., the reactive carrier is used as an additive delivery vehicle). As indicated, a reactive carrier having a molecular weight of less than about 1 Å, gram/mol can not only promote uniform blending of the additive into the polymer melt, but also with polyethylene terephthalate. The diester polymer reacts 'to ensure that the carrier does not escape in subsequent procedures. Another aspect of the invention comprises polymerizing a polyethylene terephthalate precursor via melt phase condensation polymerization to produce an intrinsic viscosity having a target of at least about 45 dl/g (i.e., an average degree of polymerization of about 7 〇). The polyethylene terephthalate water σ                               Additives are introduced. Finally, complete the polyethylene terephthalate

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Line 1249545 A7 B7 V. Description of Invention (12) Melt phase condensation polymerization of diester polymer. When an additive is introduced during the condensation polymerization of the polyethylene terephthalate polymer, the intrinsic viscosity is preferably at least about 0.50 dl/g, more preferably at least about 0.55 dl/g, and at least about 0.60. The liters/grams are optimal (i.e., the average degree of polymerization is about 80, 90, and 100, respectively). The polyethylene terephthalate polymer has sufficient molecular weight, mechanical properties, melt strength, and crystallinity to promote polymer processing at an inherent viscosity of at least about 0.45 deciliter per gram. The term "intrinsic viscosity" as used herein is the ratio of the specific viscosity of a polymer solution of known concentration to the concentration of a solute that is interpolated to zero concentration. The intrinsic viscosity, which is widely known as the standard for polymer properties, is proportional to the average polymer molecular weight. See, for example, Dictionary of Fiber and Textile Technology, Hoechst Celanese Corporation (1990); Tortora &amp; Merkel, Fairchild’s Dictionary of Textiles (7th ed. 1996). Those skilled in the art can measure and measure the inherent viscosity without undue experimentation. For the intrinsic viscosity values described here, the intrinsic viscosity is determined by dissolving the copolymerized vinegar in the original chlorine test (OCP), using the Schott Autoviscometer (AVS Schott and AVS 500 Viscosystem) to measure the relative viscosity of the solution, and then calculating the inherent viscosity based on the relative viscosity. Measured by viscosity. See, for example, the Technical Dictionary of Fibers and Textiles ("Intrinsic Viscosity"). Specifically, 0.6 g of the dried polymer sample (+ / - 0.005 g) was dissolved in about 50 ml (61.0 - 63.5 g) of prochlorophenol at a temperature of about 105 °C. The fiber and yarn samples are typically cut into small pieces while the chip sample is ground. After cooling to room temperature, place the solution at a controlled temperature (Example -15 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1249545 A7 ____B7 V. Invention Description (13) In a viscometer under 'between about 20 ° C and 25 ° C, and measure the relative viscosity. As indicated, the intrinsic viscosity is calculated from the relative viscosity. The term "diol component" is used herein primarily to refer to ethylene glycol, although other glycols (e.g., &apos;low molecular weight polyethylene glycols) may also be used. It is well known to those skilled in the art that the glycol component typically forms the majority of the end groups of the polymer chain and is therefore present in the composition at a somewhat greater ratio. For example, the molar ratio of δθ 成 及 及 and monohydric alcohol is typically between about 1 · 〇 : 1 . 〇 and 1.0: 1.6. The term "terephthalate component" as used herein refers to dibasic acids and dibasic esters which are useful in the preparation of polyethylene terephthalate. In particular, terephthalate components mainly include terephthalic acid and dimethyl terephthalate, but may also include dibasic acids and diester comonomers. In this regard, those skilled in the art will recognize that there are two conventional methods of producing 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. In this technique, the aforementioned step of reacting the terephthalate component with the glycol component comprises reacting terephthalic acid and ethylene glycol in a heated esterification reaction to form a single terephthalic acid and ethylene glycol. Body and oligomers, as well as water by-products. In order for the esterification reaction to be substantially complete, it must be continuously removed as it is formed. Other methods involve a two-step transesterification reaction and polymerization using dimethyl terephthalate and excess ethylene glycol. In the present technique, the aforementioned step of reacting the terephthalate component and the glycol component comprises reacting dimethyl terephthalate and ethylene glycol in a transesterification reaction to form a terephthalate and B-16- This paper silver scale is applicable to China National Standard (CNS) Α4 specification (210X297 public) 14 1249545 V. Invention description (monomer and oligomer of diol' and the reaction as a by-product can be basically carried out $全, in order to remove the cool cross. When it is generated, it must be known to those skilled in the art that the polyterephthalic acid described here can be a monohydric alcohol component including ethylene glycol- _ mono-nonanol, 1 3 And -_ 旰卜又—兀醉, such as two

t I-C, Μ, 丁····································································· Or the tampering of terephthalic acid or _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ On the glutinous-methyl hydrazine r on the big eve of the two industries of the poly::: one red red ethane vinegar polymer for the modified polyethylene terephthalate brewed in the heart of the day 'direct vinegar reaction is more old-fashioned The two-step brewing exchange reaction is preferred. As indicated, the direct acetification technique allows terephthalic acid and ethylene glycol to form low molecular weight monomers, oligomers, and water. ~ For example, in a typical process, continuous feed enters a direct esterification vessel operating at a temperature between about Ο and 2 nautical and at a pressure between about 5 and 85 _ Between 5 hours, this typically uncatalyzed reaction produces low molecular weight monomers, oligomers, and water. Water is removed as the acetation reaction proceeds, and excess ethylene glycol is removed, providing a favorable Reaction kinetics. Thereafter, the low molecular weight monomers and oligomers are polymerized by condensation polymerization to form a polyethylene terephthalate polyester. This condensation polymerization stage generally uses two or more containers in series, and Operating at a temperature between about 25 (rc &amp; 3 〇 5r &lt; lt.) between about 1 and 4 hours. Condensation polymerization is usually referred to as 17 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297) Binding 1249545 A7 B7 V. INSTRUCTIONS (15) Starting in the first vessel of the low polymerizer. The low polymerizer is operated at a pressure range between about 0 and 70 ton: ton. And the oligomer is condensed and polymerized to form polyethylene terephthalate and ethylene glycol. As previously indicated, the application of a vacuum removes ethylene glycol from the polymer melt to drive the reaction to completion. To this end, the polymer melt is typically agitated to promote the escape of ethylene glycol from the polymer melt. And assisting the highly viscous polymer melt to move through the polymerization vessel. When the polymer melt is supplied to the continuous vessel, the molecular weight, and thus the inherent viscosity of the polymer melt, is increased. Generally, the temperature of each vessel is increased, and The pressure is reduced to allow for greater polymerization in each of the continuous vessels. The final vessel, generally referred to as a "high polymerizer," operates at a pressure of between about 0 and 40 Torr. Like a low polymerizer, Each polymerization vessel is connected to a flash vessel and is typically agitated individually to facilitate the removal of ethylene glycol. The residence time in the polymerization vessel and the feed rate portion of the ethylene glycol and terephthalic acid entering the continuous process. It is determined based on the molecular weight of the polyethylene terephthalate polyester. Since the molecular weight can be easily determined based on the inherent viscosity of the polymer melt, the solid solution of the polymer melt is generally used. Viscosity determines the polymerization conditions, such as temperature, pressure, rate of supply of the reactants, and residence time in the polymerization vessel. Note that in addition to the formation of polyethylene terephthalate polymer, undesirable side reactions occur. Side reactions of the product. For example, esterification of ethylene glycol produces diethylene glycol (DEG) which is added to the polymer chain. As is known to those skilled in the art, diethylene glycol will result in a polymer. The softening point is reduced. In addition, a small amount of ring oligomers are produced (for example, terephthalic acid and ethylene-2-18). The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1249545 V. Description of the Invention (Polymers and tetramers). The removal of the "handle" during the formation of the condensation polymerization will reduce the formation of such by-products. = However, the previous discussion focused on the production of polyacetate to benzene: formic acid g polymer 'but the fact that this is 3 $ on the day of the month is not limited. The teachings disclosed here can be applied to use Continuous process, semi-continuous process, and even other condensation polymers of the batch process. I, I. The condensation polymer of the present invention is filtered and extruded in a molten phase to form a polymer sheet, filament, or hard. After the condensation polymerization: it is preferred that the (4) body is extruded. After extrusion, it is preferred to use water spray or immersion in the water tank to promote solidification. The cured compound is cut into chips or Granules for misplacement and handling. The term "particles" as used herein is used to indicate chips, granules, and the like. As is known to those skilled in the art, in some cases, the particles formed from the condensed poly σ and the reactive carrier can be crystallized after solid state polymerization (ssp) to increase the molecular weight of the polymer resin. It should be noted that the present invention does not adversely affect the SSP rate, and it is usually even 8 pin high. The polymer chips are then remelted and the enamel (e.g., 'shirts), filaments, films, or other application technicians are aware that the particular condensation polymer, such as the amorphous/ester, does not need to undergo SSP. ^ ^Oxamic acid A special advantage of the present invention is to reduce the polymer transition time by changing the mixed IL of the continuous process caused by the polymer formulation.举=In addition to the process of processing the vinegar from the glycol solution or adding the additive to the slurry: this: X 297 mm) -19- 1249545 A7 B7 V. Description of the invention (17) The glycol stream is added to the vinegar The method or first condensation polymerization vessel each has a high ethylene glycol content. In order to achieve a change in the product, it is necessary to completely replace the contents of each subsequent container. In a standard continuous unit, the required transition time is around 4 to 8 hours. The present invention improves upon the prior art by using a reactive carrier rather than using an inert carrier, or without the use of a carrier. The reactive carrier should be incorporated into the condensation polymer in an amount that does not significantly affect the properties of the overall polymer. The reactive carrier can be combined with the condensation polymer such that it is preferably unextractable in subsequent processing operations. The reactive carrier preferably has a melting point which ensures that it is at about 100 ° C (which can be achieved using low pressure steam). The reactive carrier has the optimum melting point to ensure that it is liquid or slurry at near ambient temperature. The term "close to the environment" as used herein includes temperatures between about 20 ° C and 60 ° C. Proximity to ambient temperature simplifies the unit operations required to introduce the additive. It does not require an extruder or a complicated heating system for introducing the reactive carrier into the condensation polymer. The reactive carrier should generally comprise no more than about 1 weight percent (i.e., 10,000 ppm) of the polymeric resin. The reactive carrier is preferably incorporated into the condensation polymer in an amount 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 a concentration in the polymer resin of less than 500 ppm (i.e., 0.05 weight percent) will further reduce the potential adverse effect on the overall polymer properties. Figures 1 and 2 illustrate the theoretical loss of molecular weight (as measured by the number average degree of polymerization) as a function of the concentration of the reactive carrier at different molecular weights. Figure 1 -20- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1249545

AT B7 V. INSTRUCTION DESCRIPTION (18) The effect of a reactive carrier on a condensation polymer having an initial degree of polymerization of about 100 is depicted. Similarly, Figure 2 depicts the effect of a reactive support on a condensation polymer having an initial degree of polymerization of about 70. (For polyethylene terephthalate, a polymerization degree of about 100 corresponds to an intrinsic viscosity of about 0.61 dl/g, and a polymerization degree of about 70 corresponds to an intrinsic viscosity of about 0.45 dl/g.) Note that in any condensation At higher concentrations in the polymer resin, the higher molecular weight reactive carrier has less adverse effect on the average degree of polymerization of the polymer resin. Similarly, Figures 3 and 4 illustrate the theoretical loss of intrinsic viscosity as a function of the concentration of the reactive carrier at several molecular weights. Figure 3 depicts the effect of a reactive support on polyethylene terephthalate having an intrinsic viscosity of 0.63 dl/g. Similarly, Figure 4 depicts the effect of the reactive support on polyethylene terephthalate having an inherent viscosity of 0.45 dl/g. As is apparent to those skilled in the art, macromolecules having a degree of polymerization of about 70 are considered to be high polymers. For polyethylene terephthalate, this roughly corresponds to a molecular weight of at least about 13,000 grams per mole. At this molecular weight, the polyethylene terephthalate polymer has molecular weight, mechanical properties, melt strength, and crystallinity sufficient to promote polymer processing. In contrast, the reactive carrier according to the present invention has a molecular weight of less than about 10,000 grams per mole. The molecular weight of the reactive carrier is typically less than 6000 g/mole, preferably less than 4000 g/mol, more preferably between about 300 and 2000 g/mol, and at about 400 and 1000 g/m. The best between the ears. The molecular weight as used herein refers to a number average molecular weight, rather than a weight average molecular weight. In general, a reactive carrier having a carboxyl group, a hydroxyl group, or an amine functional group is preferred. Appropriate reactive carriers include in the solid state polymerization process can be combined with the condensation - 21 paper size of the Chinese National Standard (CNS) A4 specifications (210X297 mm) 1249545 V, invention description (19 A7 B7 ^ material reaction, without It will cause the condensation polymer to undergo molecular weight loss in the subsequent heating process, including the derivatization of the amine (including the derivatized 低 <low-compound) amide (including the oligomerization of the derivatization of its own decylamine). ":), brewed imine, amine, isocyanic acid vinegar", acid, and liver.... Poly 1 is enough to make the molecule so that the polyol will not substantially condense, Ai average knife I lower, and has Promoting the pumping of polyols: Polyols, especially polyhydric alcohols and polyether polyols are preferred. Yongyi-alcohol is a preferred guest; two containing 々_^ 夕凡醉. Other examples of the alcohol include a functional group such as polypropylene glycol prepared from % oxypropane, a random and block copolymer of ethylene oxide and cyanoacrylate, and a polymerization derived from tetrahydrogen. Polybutanediol. The hydrazine or 'reactive carrier may also include dimers or trimers. And an anhydride. In the embodiment, the reactive carrier may have an internal functional group (eg, ester, oxime) that reacts with the condensation polymer in addition to or instead of the amine. In an embodiment, the reactive carrier may be reacted into the condensation polymer during solid state polymerization, and the molecular weight loss of the condensation polymer will not be caused in the injection molding or t Wan method. An anthracene having no functional end groups, or an anhydride having no functional end, as indicated and as known to those skilled in the art, derived from 匕 田 杂 ( (eg, caprolactone and caprolactam) Reactive carriers are within the scope of the invention. ... When it is known that the additives are sometimes sold as oligomers constituting an acceptable reactive carrier. For example, TINUVIN 2 13 from Ciba Specialty Chemicals includes hydroxyphenyl groups. Benzotriazole ultraviolet light absorber dissolved in molecules

1249545 A7 B7 V. Description of invention (20

The amount is 300 g/mole in a solution of unreacted polyethylene glycol. As previously discussed, polyethylene glycol is the preferred reactive carrier. Accordingly, the present invention contemplates the use of such premixed additives/reactive carrier products. An example of a process according to the invention comprises reacting terephthalic acid and ethylene glycol in a heated esterification reaction to form monomers and oligomers of terephthalic acid and ethylene glycol, and then making such a single The bulk and oligomer are polymerized by melt phase condensation polymerization to form a polyethylene terephthalate polymer. It uses a reactive carrier to introduce the additive into the polyethylene terephthalate polymer, which aids in uniform mixing within the polymer solution. Reactive carrier ties = allows the polyol to be pumped at near ambient temperature (ie below 6 〇. [ ]): a polyol (eg, polyethylene glycol), and which does not significantly affect the permanent benzene The amount of the overall nature of the ethylene glycol dicarboxylate polymer is preferably introduced to the poly(p-phenylene) acid B. The polyethylene terephthalate polymer is then formed into chips (or formed into pellets using a polymer cutter) prior to solid state polymerization. The focus is on the polyol-reactive carrier and the polyethylene terephthalate so that it is not extractable in subsequent processing operations (eg, forming a polyester beverage container). As indicated, the invention includes the use of reactivity. Later in the carrier, various additives are added: when the additive is volatile or thermally degraded, especially in the later stage: 2. It is known that the additive is injected before the condensation polymerization, such as in polyester (esterification in polyester) In the stage, or in the early stage of the condensation polymerization stage, the === high temperature (greater than the assignment) and decompression (below the hop) conditions of the hour of employment. Therefore, in these conditions, the corpse will be lost from the program. The square pressure of the Ming (additive. Another month) "French method significantly reduces the amount of additives. The paper scale is applicable to China National Standard (CNS) A4 regulation binding line -23 1249545 A7 B7 21 V. Invention description (High to high condensation polymerization temperature) The additive according to the present invention may include a preform heating rate enhancer, a friction reducing additive, a stabilizer, an inert particulate additive (for example, clay or oxidized stone), a colorant, Oxidizer, branching agent, oxygen barrier agent, carbon dioxide blocker, oxygen scavenger, flame retardant, crystallization control agent 'acetaldehyde reducing agent, impact modifier, catalyst deactivator, melt strength improver, antistatic Agents, lubricants, chain extenders, nucleating agents, solvents, fillers, and plasticizers. In a preferred embodiment, the additive is ultraviolet (uv) radiation absorption: as understood by those familiar with polyester packaging The uv absorber protects the polybutylene-ethylene formate polymer and the contents of the package from degradation (10). In another preferred embodiment, the 'additive is an inert particulate additive, T talc (ie, represents a chemical formula of 3Mg0, 4Si〇2.H2〇 is a natural water-containing stone or sink; the temple is carbonated Laijia. The inert particle additive is about 20 and 2 GGppm at a low concentration (ie, the combined weight of the condensation polymer, the reactive carrier, and the inert particulate additive). Introduced to ensure that it is formed from a condensation polymer:: has: low friction properties. In addition, 'surface treatment to minimize the minimum inert particle additives in the bottle to have an average lower than _ micro Large particles Preferably, it is preferably less than 2 micrometers. As described in U.S. Patent Application Serial No., 9/738,619, the bottle formed from such a poly-pair =-^ ethylene II condensation polymer has improved The friction can be reduced, and the need to fill the lubricant can be eliminated. "In the outer coating of the leeches, in the other preferred embodiment, the size of the nano-replicated paper of the additive-exfoliated clay适 _ _ 24 1249545 A7 B7 5, invention description (22), which can improve the gas barrier properties in the film and container. The nanocomposite is a small plate shape with a thickness of about 6 and 15 angstroms. Preferably, as is known to those skilled in the art, polymeric catalysts can increase the rate of polymerization and thereby increase productivity. Unfortunately, these same catalysts will eventually degrade the thermal stability of the polymer resin. Thus, in yet another preferred embodiment, the additive carried by the reactive carrier is a catalyst stabilizer. Although a phosphorus-containing stabilizer is preferred, any stabilizer which deactivates the polymeric catalyst can be introduced via the reactive carrier. In general, the stabilizer should not react with the polymer and have low residual moisture. U.S. Patent Application Serial No. 09/738,150 teaches that when the condensation polymerization of polyethylene terephthalate is nearly complete, the catalyst begins to form acetaldehyde and causes discoloration or yellowing of the polyethylene terephthalate. Thus, as discussed herein, heat stable polyester refers to a polyester having a low acetaldehyde content, low discoloration, and high molecular weight retention despite exposure to elevated temperatures. An undesirable by-product of the degradation of acetaldehyde-based polyethylene terephthalate. This is a particular concern of the food and beverage industry, as even small amounts of acetaldehyde can adversely affect the odor of the product. In addition, polymer degradation typically causes undesirable discoloration or yellowing. This is why the stabilizer (preferably containing phosphorus) is added to the polymer melt. The late addition of the stabilizer to the polymer melt advantageously prevents the stabilizer from inhibiting ("cooling") the polymerization catalyst during the condensation polymerization. This improves the production efficiency of the continuous polyethylene terephthalate process. Further, since the stabilizer is added before the processing of the polymer, the stabilizer can appropriately prevent discoloration and degradation of the polyethylene terephthalate polyester. -25- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm).

Line 1249545 A7 B7 V. INSTRUCTIONS (23) Finally, it should be noted that the melting and extrusion steps in the formation of the condensation polymer are at high temperatures (for example, for polyethylene terephthalate, typically greater than 260 ° C) The next step is carried out so that the condensation polymer should be thermally stable. Therefore, it is necessary to properly blend the stabilizer with the polymer melt to deactivate the polymerization catalyst. The reactive carrier facilitates the addition of the stabilizer to the polymer resin. Exemplary embodiments of the invention have been disclosed in the specification and drawings. Specific terms are used only in a generic and illustrative manner and are not intended to be limiting. The scope of the present invention is described in the following claims. -26- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

Patent application No. 12495^5^91113492* A8 Chinese patent application scope replacement (^4 years 9曰, B8 * &quot;一'- ----. J ' j)8 Patent application scope 1. A kind of additive introduction A The method in the process of sb human inclusion · soil '5 polymer, the condensation polymerization of carbonyl ruthenium through the melt phase 】...polymerization of oligomeric precursors to form a polymer having an acid group g to form a sexual foot condensation polymer; ', in 2 gram / Mo and 1 〇, 〇〇〇 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / A delivery vehicle for the additive. 2. According to the method of claim 1, the step of combining the oligomeric precursors comprises polymerizing the oligomeric precursors via melt phase condensation polymerization to form an average having a carbonyl functionality and at least about ^ The degree of polymerization of the condensation polymer; and/or more than the step of introducing the reactive carrier into the condensation polymer, completes the melt phase condensation polymerization of the condensation polymer. 3. The method of claim 2, wherein the condensation polymer has a target average degree of polymerization of at least about 80. Wherein the condensation polymer is further included in the condensation polymer. The average degree of polymerization is at least about 90% according to the method of the second aspect of the patent application. 5. The method according to the method of claim 2, the average degree of polymerization is at least about 100. 6. Prior to the step of polymerizing the oligomeric precursor by phase condensation polymerization according to the method of claim 1 of the patent application, the first polycyclic component is reacted to form an oligomeric precursor of the condensation polymer. / 7. According to the method of claim 6, wherein the first multi-functional paper scale is applicable to the Chinese National Standard (CNS) a4 specification (21〇) &lt; 297 mm) 1249545 A8 B8 C8 D8 VI. Application The step of reacting the components of the patent range with the di-polyfunctional component involves reacting the dibasic acid with the diol to form an oligomeric precursor. 8. The method of claim 6, wherein the step of reacting the first polyfunctional component and the second polyfunctional component comprises reacting the dibasic ester and the glycol to form an oligomeric precursor. 9. The method of claim 6, wherein the step of reacting the first polyfunctional component and the second polyfunctional component comprises reacting a diisocyanate with a glycol to form an oligomeric precursor. 10. The method of claim 6, wherein the step of reacting the first polyfunctional component and the second polyfunctional component comprises reacting a diol and a carbonic acid derivative to form an oligomeric precursor. 11. The method of claim 6, wherein the step of reacting the first polyfunctional component and the second polyfunctional component comprises reacting the dibasic acid with the diamine to form an oligomeric precursor. 12. The method of claim 6, wherein the step of reacting the first polyfunctional component and the second polyfunctional component comprises reacting the dianhydride and the diamine to form an oligomeric precursor. 13. The method of claim 1, wherein the step of polymerizing the oligomeric precursor via melt phase condensation polymerization comprises self-polymerizing a monomer having polyfunctionality to produce a condensation polymer having a carbonyl functionality. M. The method of claim 2, wherein the reactive carrier is introduced into the condensation polymer in an amount that does not significantly affect the overall polymer properties of the condensation polymer. 15. The method of claim i, wherein the reactive carrier package 1249545 A8 B8 C8 D8 is in the form of a polyol having a molecular weight of between 30,000 g/mol and 10,000 g/mol. 16. The method of claim 5, wherein the polyol comprises polyethylene glycol. 17. The method of claim i, wherein the reactive carrier is selected from the group consisting of esters, guanamines, quinones, amines, isocyanates, oxazolines, acids, and anhydrides. 18. The method of claim i, further comprising forming the condensation polymer and the reactive carrier as chips or particles. 19. The method according to any one of claims 1-6, which further comprises forming the condensation polymer and the reactive carrier into a chip, and wherein the inclusion of the polymer and the reaction The carrier is solid state polymerized. Further includes; it further includes J. Further includes: 21. The method according to any one of claims 丨-丨8, wherein the condensation polymer and the reactive carrier are formed into a container. 22. The method according to any one of the claims of the invention, wherein the condensation polymer and the reactive carrier are drawn into fibers. 2 3 · Method according to the scope of the patent application 丨_丨8 任 项 Item The condensation polymer and the reactive carrier are formed into a film. / (4) According to the patent No. _8 or the middle material (four) circumference ΐ3·ΐ8 壬—the “Wan method, wherein the condensation polymer includes polyester. 25. According to the scope of application for patents No. ι_6, the scope of the ninth patent range, or the scope of the pi patent range No. 1 3 - 18. Ancient 廿,,,, &quot; 凡法, where the condensation The polymer includes a polyurethane. -3- 1249545 The method of claim </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; =: The method of claiming the patent scope of the invention, the method of claim 6, the method of claiming the patent scope, or the method of claim 13, wherein the condensed poly-δ substance comprises polyamine. The method of claim 6, wherein the condensed polymer comprises polyamidiamine, or the method of claim 13, wherein the condensed polymer comprises a polyimine. 29. The method of claim </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; 30. The method according to any one of the preceding claims, wherein the reactive carrier is liquid or condensed at near ambient temperature. The method of claim 3, wherein the reactive carrier is introduced into the condensation polymer in an amount such that its concentration in the condensation polymer is less than about 10,000 Ppm. The method according to any one of the preceding claims, wherein the reactive carrier is introduced into the condensation polymer in an amount such that its concentration in the condensation polymer is less than about 5% by weight. The method of the present invention, wherein the concentration in the reaction is less than about 500. 33. According to the patent application, any of the carriers is introduced into the condensation polymer in an amount of ppm of the condensation polymer. Wherein the reaction 34. According to the scope of the patent application 丨·丨8, only &lt; method carrier has a knife of less than about 6000 g / mole 0 4- A8 B8 C8 r»c The method of claim 18, wherein the reactive carrier has a molecular weight of less than about 4000 g/mole. 36. According to the scope of the patent application, the reactive carrier has a molecular weight of between about 300 and 2000 g/mol. 37. According to the method of the bl8 term of the patent scope The reactive carrier has a molecular weight of between about 40 Torr and 1000 g/mol. 38. The method of any one of claim 18, wherein the reactive carrier comprises a polyol 39. The method according to any one of claims 丨 丨 丨 丨 或 或 或 或 或 或 或 或 & & & & & & & & & & & & & & & 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应And a group consisting of a trimer anhydride. 40. According to the patent application scope 丨 丨 丨 4 or the patent application 丨 8 item, wherein the reactive carrier is a derivative or a caprolactone Or a method of any one of the above-mentioned claims, wherein the reactive carrier is selected from the group consisting of esters, decylamines, quinones, amines, a group of isocyanates, oxazolines, acids, and anhydrides, The reactive carrier can react with the condensation polymer during solid state polymerization without degrading the molecular weight of the condensation polymer in subsequent heating polymer procedures. 42' According to any of the patent scopes 1 - 18 The method, wherein the one or more additives comprise a UV absorber. The method according to any one of the preceding claims, wherein the one or more additive comprises an additive for increasing the heating rate of the preform. Laijia Standard (CNS) A4 Specification ((10) χ 公 公 公) 1249545 申凊专利范园 44_ According to the method of "Special (4)® 1] (4) - Item A variety of additives include phosphorus stabilizer. 45. According to the method of the patent range No. 1·18, the various additives include oxygen scavengers. 46. According to the method of any one of the claims 1-1 8 of the patent application, various additives include exfoliated clay 亳 microcomposites. 47: According to any one of the methods of claim 1 or claim 8, the method comprises the steps of: adding a sputum to a sputum, and adding the additive comprising between about 2 〇 and 2 〇〇 ppm selected from the group consisting of talc and calcium silicate. A group of inert particulate additives having an average particle size of less than about 10 microns. 48. The method of claim 47, wherein the inert particulate additive is surface modified. 9. The method according to any one of the preceding claims, wherein the one or more additives comprise a component selected from the group consisting of a friction reducing additive, a stabilizer, an inert particulate additive, a colorant, an antioxidant, a branching agent, and a barrier. Agent, flame retardant, crystallization control agent, acetaldehyde reducing agent, impact modifier, catalyst deactivator, melt strength improver, antistatic agent, lubricant, chain extender, nucleating agent, solvent, filler, And the additive of the group consisting of plasticizers, wherein one or one of the one or the other of the one or -6 - the paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm)