Source: http://www.google.com/patents/US7759449?dq=5579430
Timestamp: 2017-07-20 17:33:52
Document Index: 460086834

Matched Legal Cases: ['Application No. 2', 'Application No. 2', 'Application No. 2431823', 'Application No. 2', 'Application No. 2431637', 'Application No. 090131091', 'Application No. 090131091', 'Application No. 091112797', 'Application No. 091112797', 'Application No. 091113492', 'Application No. 091113492', 'Application No. 01992116', 'Application No. 01992116']

Patent US7759449 - Methods for introducing additives into polyethylene terephthalate - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsThe invention is a method for the late introduction of additives into polyethylene terephthalate. The method employs a reactive carrier that functions as a delivery vehicle for one or more additives. The reactive carrier reacts with the polyethylene terephthalate, thereby binding the reactive carrier...http://www.google.com/patents/US7759449?utm_source=gb-gplus-sharePatent US7759449 - Methods for introducing additives into polyethylene terephthalateAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS7759449 B2Publication typeGrantApplication numberUS 10/962,167Publication dateJul 20, 2010Filing dateOct 8, 2004Priority dateDec 15, 2000Fee statusPaidAlso published asUS7858731, US20050170175, US20070142537, US20080226856Publication number10962167, 962167, US 7759449 B2, US 7759449B2, US-B2-7759449, US7759449 B2, US7759449B2InventorsCarl S. Nichols, Tony Clifford MooreOriginal AssigneeWellman, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (103), Non-Patent Citations (51), Referenced by (2), Classifications (50), Legal Events (11) External Links: USPTO, USPTO Assignment, EspacenetMethods for introducing additives into polyethylene terephthalate
US 7759449 B2Abstract
The invention is a method for the late introduction of additives into polyethylene terephthalate. The method employs a reactive carrier that functions as a delivery vehicle for one or more additives. The reactive carrier reacts with the polyethylene terephthalate, thereby binding the reactive carrier in the polyethylene terephthalate resin and preventing the emergence of the reactive carrier and additives from the polyethylene terephthalate during subsequent thermal processing.
1. A method for introducing additives into polyethylene terephthalate, comprising:
polymerizing polyethylene terephthalate precursors via melt phase polycondensation to form polyethylene terephthalate polymers possessing sufficient molecular weight to facilitate polymer processing; and
thereafter, introducing an additive into the polyethylene terephthalate polymers via a reactive carrier that has a molecular weight of between about 300 and 10,000 g/mol, the reactive carrier being a delivery vehicle for the additive;
wherein the additive is introduced to the polyethylene terephthalate polymers in quantities such that its concentration in the polyethylene terephthalate polymers is less than about one weight percent; and
wherein the reactive carrier is introduced to the polyethylene terephthalate polymers in quantities such that bulk properties of the polyethylene terephthalate polymers are not significantly affected.
6. A method according to claim 1, wherein the step of polymerizing polyethylene terephthalate precursors comprises polymerizing polyethylene terephthalate precursors via melt phase polycondensation to form polyethylene terephthalate polymers having an intrinsic viscosity of at least about 0.45 dl/g.
7. A method according to claim 1, wherein the step of polymerizing polyethylene terephthalate precursors comprises polymerizing polyethylene terephthalate precursors via melt phase polycondensation to form polyethylene terephthalate polymers having an intrinsic viscosity of at least about 0.50 dl/g.
8. A method according to claim 1, wherein the step of polymerizing polyethylene terephthalate precursors comprises polymerizing polyethylene terephthalate precursors via melt phase polycondensation to form polyethylene terephthalate polymers having an intrinsic viscosity of at least about 0.55 dl/g.
9. A method according to claim 1, wherein the step of polymerizing polyethylene terephthalate precursors comprises polymerizing polyethylene terephthalate precursors via melt phase polycondensation to form polyethylene terephthalate polymers having an intrinsic viscosity of at least about 0.60 dl/g.
18. A method according to claim 1, wherein the additive is selected from the group consisting of heat-up rate enhancers, inert particulate additives, colorants, antioxidants, branching agents, barrier agents, oxygen scavengers, 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.
25. A method for introducing additives into polyethylene terephthalate, comprising:
wherein the reactive carrier is introduced to the polyethylene terephthalate polymers in quantities such that its concentration in the polyethylene terephthalate polymers is less than about 1,000 ppm.
32. A method according to claim 25, wherein the additive is selected from the group consisting of heat-up rate enhancers, inert particulate additives, colorants, antioxidants, branching agents, barrier agents, oxygen scavengers, 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.
33. A method for the late introduction of compatibilizer into polyethylene terephthalate, comprising:
polymerizing the polyethylene terephthalate precursors via melt phase polycondensation to form polyethylene terephthalate polymers; and
thereafter introducing a compatibilizer into the polyethylene terephthalate polymers via a reactive carrier having a molecular weight of less than about 10,000 g/mol, the reactive carrier being a delivery vehicle for the compatibilizer.
the step of polymerizing polyethylene terephthalate precursors comprises polymerizing polyethylene terephthalate precursors via a continuous melt phase polycondensation process to form a polyester melt comprising polyethylene terephthalate polymers; and
the step of introducing an additive into the polyethylene terephthalate polymers via a reactive carrier comprises introducing an additive into the polyester melt via a reactive carrier.
41. A method according to claim 25, wherein:
the step of introducing an additive into the polyethylene terephthalate polymers via a reactive carrier comprises introducing an additive into the polyester melt via a reactive carrier such that the reactive carrier reacts with the polyethylene terephthalate polymers.
This application is a continuation-in-part of commonly-assigned U.S. application Ser. No. 10/628,077, now U.S. Pat. No. 6,803,082, for Methods for the Late Introduction of Additives into Polyethylene Terephthalate, which was filed Jul. 25, 2003, and which itself is a continuation of commonly-assigned U.S. application Ser. No. 09/738,150, now U.S. Pat. No. 6,599,596, for Methods of Post-Polymerization Injection in Continuous Polyethylene Terephthalate Production, which was filed Dec. 15, 2000. Both U.S. Pat. No. 6,803,082 and U.S. Pat. No. 6,599,596 are herein incorporated by reference in their entirety.
This application, like its parent applications, incorporates entirely by reference commonly-assigned application Ser. No. 09/738,619, now U.S. Pat. No. 6,500,890, for Polyester Bottle Resins Having Reduced Frictional Properties and Methods for Making the Same.
This application further incorporates entirely by reference the following commonly-assigned patents and patent applications: Ser. No. 09/932,150, for Methods of Post-Polymerization Extruder Injection in Polyethylene Terephthalate Production, filed Aug. 17, 2001, now U.S. Pat. No. 6,569,991; Ser. No. 10/017,612, for Methods of Post-Polymerization Injection in Condensation Polymer Production, filed Dec. 14, 2001, now U.S. Pat. No. 6,573,359; Ser. No. 10/017,400, for Methods of Post-Polymerization Extruder Injection in Condensation Polymer Production, filed Dec. 14, 2001, now U.S. Pat. No. 6,590,069; Ser. No. 10/176,737 for Polymer Resins Having Reduced Frictional Properties, filed Jun. 21, 2002, now U.S. Pat. No. 6,727,306; Ser. No. 10/177,932 for Methods for Making Polyester Bottle Resins Having Reduced Frictional Properties, filed Jun. 21, 2002, now U.S. Pat. No. 6,710,158; U.S. patent application Ser. No. 10/850,269, for Methods of Making Titanium-Catalyzed Polyester Resins, filed May 20, 2004, and published Nov. 24, 2005, as U.S. Patent Application Publication No. 2005/0261462, now abandoned; and U.S. patent application Ser. No. 10/850,918, for Slow-Crystallizing Polyester Resins, filed May 21, 2004, now U.S. Pat. No. 7,129,317.
Before 1965, the only feasible method of producing polyethylene terephthalate polyester was to use dimethyl terephthalate (DMT). In this technique, dimethyl terephthalate and ethylene glycol are reacted in a catalyzed ester interchange reaction to form bis(2-hydroxyethyl) terephthalate monomers, as well as a methanol byproduct that is continuously removed. These bis(2-hydroxyethyl)terephthalate monomers are then polymerized via polycondensation to produce polyethylene terephthalate polymers.
The invention is a novel 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. In particular, 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. This prevents the emergence of the carrier from the polyethylene terephthalate during subsequent processing, such as solid state polymerization and injection molding operations. This also improves dispersion of the additive in the polymer and reduces the tendency of the additive to emerge and deposit in polymer processing equipment during solid state polymerization.
The other method involves a two-step ester exchange reaction and polymerization using dimethyl terephthalate and excess ethylene glycol. In this technique, 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 of terephthalate and ethylene glycol, as well as methanol as a byproduct. To enable the ester exchange reaction to go essentially to completion, the methanol must be continuously removed as it is formed.
Additives according to the present invention can include preform heat-up rate enhancers, stabilizers, compatibilizers, inert particulate additives (e.g., clays or silicas), colorants, antioxidants, branching agents, oxygen barrier agents, carbon dioxide barrier agents, oxygen scavengers, 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.
In view of the foregoing, those having ordinary skill in the art will recognize the effectiveness of introducing stabilizers in accordance with the present invention. In this regard, two exemplary classes of stabilizers include ultraviolet (UV) stabilizers and catalyst stabilizers.
UV stabilizers include UV radiation absorbers. As will be understood by those familiar with polymeric packaging materials, UV absorbers protect polyester packaging (e.g., containers and films) and contents of packages from UV degradation. In brief, UV absorbers absorb UV radiation and dissipate it as thermal energy. Benzotriazole (and its derivatives) and benzophenone (and its derivatives) are exemplary UV radiation absorbers.
UV stabilizers also include hindered amine compounds. Unlike UV absorbers, hindered amine compounds do not absorb light but rather retard degradation reactions caused by UV radiation. Though their specific stabilizing mechanism is complex, hindered amines generally work by slowing photochemically initiated degradation reactions. Hindered amines are typically derivatives of 2,2,6,6-tetramethyl piperidine.
Regarding catalyst stabilizers, those having ordinary skill in the art will appreciate that polymerization catalysts increase polymerization rates, and thus 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. While phosphorous-containing catalyst stabilizers are preferred, any catalyst stabilizer that will deactivate the polymerization catalyst may be introduced via a reactive carrier. In general, the catalyst stabilizer should be non-reactive with the polymer and possess low residual moisture.
Acetaldehyde is an objectionable byproduct of polymer 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 catalyst stabilizer, preferably containing phosphorous, is added to the polymer melt.
Advantageously, the late addition of the catalyst stabilizer to the polymer melt prevents the catalyst stabilizer from inhibiting (“cooling”) the polymerization catalyst during the polycondensation reaction. This increases the production efficiency of the continuous polyethylene terephthalate process. Furthermore, because the catalyst stabilizer is added before polymer processing, the catalyst stabilizer can adequately prevent discoloration and degradation of the polyethylene terephthalate polyester.
Those having ordinary skill in the art will understand that acetaldehyde can be further reduced according to the present invention by introducing acetaldehyde reducing agents (i.e., acetaldehyde scavengers) in conjunction with catalyst stabilizers, such as phosphorous-containing stabilizers. For example, in accordance with the present invention, the acetaldehyde reducing agent and the catalyst stabilizer may be introduced together via reactive carrier during melt polycondensation (e.g., where the intrinsic viscosity of the polyethylene terephthalate polymers is about 0.45 dl/g or more) or after melt polycondensation stage. Moreover, in accordance with the present invention, the acetaldehyde reducing agent may be introduced via reactive carrier during melt polycondensation and the catalyst stabilizer may be introduced via reactive carrier after melt polycondensation, or vice-versa.
It should be noted that because the melting and extruding steps in the formation of the polyethylene terephthalate polyester are performed at elevated temperatures (e.g., usually greater than 260° C.), it is important that the polyethylene terephthalate be thermally stable. Accordingly, the catalyst stabilizer additive must be adequately blended with the polymer melt to deactivate polymerization catalysts. The reactive carrier facilitates the incorporation of the catalyst stabilizer into the polymer resin.
As noted, compatibilizers may be introduced to polyethylene terephthalate in accordance with the present invention. Compatibilizers are employed to make homogenous polymer blends from polymers that are, at least in some respects, incompatible. Such compatibilized polymer blends can possess unique, desirable properties and can reduce the need for expensive and time-consuming development of new polymers. Compatibilizers can also be used as polymer modifying agents to improve such properties as impact strength, tensile strength, and chemical resistance.
An exemplary use of compatibilizers is described in U.S. Pat. No. 6,339,121, which is herein incorporated by reference in its entirety. For instance, U.S. Pat. No. 6,339,121 describes blending immiscible polymers to improve the polymer blend. U.S. Pat. No. 6,339,121 specifically discloses a nanocomposite compatibilizer that is formed by combining an organoclay and an intercalation agent. As used herein, however, the term “compatibilizer” is used in its broad sense and is in no way limited to the kinds of compatibilizers described in U.S. Pat. No. 6,339,121.
Modifying polyethylene terephthalate with compatibilizers can increase its intimacy with other kinds of polymers. In this regard, compatibilized polyethylene terephthalate may be blended with other condensation polymers, such as polyamides (i.e., nylons), polyimides, polyurethanes, and polycarbonates. Compatibilizers may also be used with other polyesters, such as polytrimethylene terephthalate and polybutylene terephthalate.
In addition, compatibilized polyethylene terephthalate may be blended with addition polymers, such as olefins (e.g., high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and polypropylene), chlorinated polymers (e.g., polyvinylchloride (PVC) and polyvinyl dichloride (PVDC)), and fluorinated polymers (e.g., polyvinyl fluoride (PVF) and polyvinylidene difluoride (PVDF)). Polymer blends that include compatibilized polyethylene terephthalate (i.e., prepared in accordance with the present invention) may be may be especially useful in containers, films, and engineering resins, as well as in textiles, such as fibers, yarns, and fabrics (e.g., nonwovens).
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No. 6,573,359.23English translation of Taiwanese Office Action in commonly owned copending Taiwanese Application No. 091113492, Counterpart of U.S. Appl. No. 6,573,359, issued on Jul. 4, 2005 [Re-cited with date as requested by Examiner].24European Office Action for corresponding European Application No. 01992116, dated Jan. 9, 2004.25European Office Action in corresponding European Patent No. 1341836, dated Jan. 9, 2004.26G.M. Terekhova, N.V. Mikhailov, L.G. Tokareva; Heat Stability of Polyethylene Terephthalate (PET) Containing Phosphoric Acid Esters; Khimicheskie Volokna, No. 4, 1964, pp. 33-35.27International Search Report (mailed Jun. 14, 2002), Written Opinion (mailed Aug. 7, 2002), Written Opinion (mailed Mar. 10, 2003), International Preliminary Examination Report (mailed Apr. 30, 2003), and International Preliminary Examination Report (mailed Jun. 16, 2003) for International Application No. PCT/US 01/48440.28International Search Report (mailed Jun. 6, 2002), Written Opinion (mailed Sep. 10, 2002), Written Opinion (mailed Mar. 10, 2003), and International Preliminary Examination Report (mailed Apr. 14, 2003) for International Application No. PCT/US 01/48423.29Letter from opponent Ciba in European opposition proceedings (German language) against European Patent No. 1349884, dated Aug. 20, 2007.30Letter from opponent Ciba in opposition proceedings (German-language) against European Patent No. 1341836, dated Feb. 16, 2009 [All references previously cited].31Letter from opponent Eastman Chemical Co. in opposition proceedings against European Patent No. 1341836, dated Feb. 23, 2009.32Minutes of oral proceedings before the European Patent Office (Opposition Division) for European Patent No. 1341836, dated Jan. 30, 2008.33Minutes of oral proceedings before the European Patent Office (Opposition Division) for European Patent No. 1349884, dated Nov. 7, 2007.34Minutes of the oral proceedings before the European Patent Office (Opposition Division) for European Patent No. 1349884, dated Nov. 20, 2007.35Notice of Appeal filed by Wellman against the decision to revoke European Patent No. 1349884, dated Jan. 28, 2008.36Observations on Behalf of the Patentee filed on Dec. 6, 2004 in support of European Patent No. 0 900 247. (See Cite No. 71).37Opposition Brief filed in the European Patent Office by Ciba Speciality Chemical on Dec. 8, 2005 against European Patent No. 1341836 (English translation of Cite No. 81).38Opposition Brief filed in the European Patent Office by Ciba Speciality Chemical on Dec. 8, 2005 against European Patent No. 1341836.39Opposition Brief filed in the European Patent Office by Ciba Speciality Chemical on May 23, 2005 against European Patent No. 1349884. (English translation is included).40Opposition Brief filed in the European Patent Office by Eastman Chemical Co. on May 25, 2005 against European Patent No. 1349884.41Opposition Brief filed in the European Patent Office in European Patent Office By Eastman Chemical Co. on Dec. 8, 2005 against European Patent No. 1341836.42Opposition Brief filed in the European Patent Office on Jun 23, 2004, by Eastman Chemical Co. against European Patent EP 0 900 247, which issued Sep. 24, 2003, to Wellman, Inc.43Responsive comments filed in the European Patent Office on May 5, 2006, by Eastman Chemical Co. against European Patent EP 1 349 884, which issued Aug. 25, 2004, to Wellman, Inc.44Statement of Grounds for Appeal in counterpart European Patent Application No. 01992116, filed on Jul. 25, 2008.45Summons to Oral Proceedings in European opposition proceeding against European Patent No. 1341836, dated Nov. 29, 2007.46Summons to Oral Proceedings in European opposition proceeding against European Patent No. 1349884, dated Sep. 7, 2007.47Wellman's Notice of Appeal against the decision of the Opposition Division revoking European Patent No. 1341836, dated May 30, 2008.48Wellman's Observation on Behalf of the Patentee in the Matter of European Patent No. 1349884 and in the matter of Opposition thereto by Eastman and by Ciba Spec. Chemical.49Wellman's Observations on Behalf of the Patentee in the Matter of European Patent No. 1341836 and in the Matter of Opposition thereto by Eastman and by Ciba Spec. Chemical; filed Jul. 24, 2006.50Wellman's Observations to the Oral Proceedings in the matter of European Patent No. 1341836, dated Nov. 29, 2007.51Wellman's Observations to the Oral Proceedings in the matter of European Patent No. 1349884, dated Sep. 7, 2007.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS8020784 *Oct 6, 2006Sep 20, 2011Durr Systems Inc.Coating material supply installation and associated operating procedureUS20070082143 *Oct 6, 2006Apr 12, 2007Durr Systems, Inc.Coating material supply installation and associated operating procedure* Cited by examinerClassifications U.S. Classification528/272, 528/271, 428/364, 264/176.1, 528/487, 524/115, 524/481, 528/503, 528/491, 428/36.3, 528/286, 525/437, 264/219International ClassificationC08G64/42, C08G64/20, C08G63/80, C08G63/91, C08J3/22, C08G69/48, C08G69/04, C08L67/02, C08G63/78, C08G69/28, C08J3/205, C08G63/00Cooperative ClassificationC08G64/42, Y10T428/1352, C08J3/226, C08G64/20, C08G63/91, C08G63/80, Y10T428/2913, Y10T428/1369, B29K2105/0002, C08G69/48, C08L67/02, C08G69/04, C08J3/2056, C08G63/78, C08J2367/02, C08G69/28, Y10T428/29, C08K3/34European ClassificationC08J3/205D2, C08L67/02, C08K3/34, C08G69/28, C08G69/04, C08G69/48, C08G63/78Legal EventsDateCodeEventDescriptionJul 21, 2005ASAssignmentOwner name: WELLMAN, INC., SOUTH CAROLINAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NICHOLS, CARL S.;MOORE, TONY CLIFFORD;REEL/FRAME:016843/0677Effective date: 20050616Nov 16, 2006ASAssignmentOwner name: DEUTSCHE BANK TRUST COMPANY AMERICAS, AS AGENT, NEFree format text: SECURITY AGREEMENT;ASSIGNORS:WELLMAN, INC.;FIBER INDUSTRIES, INC., A CORP. 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