WO2005103110A2 - Methods of making titanium-catalyzed polyethylene terephthalate resins - Google Patents
Methods of making titanium-catalyzed polyethylene terephthalate resins Download PDFInfo
- Publication number
- WO2005103110A2 WO2005103110A2 PCT/US2004/039726 US2004039726W WO2005103110A2 WO 2005103110 A2 WO2005103110 A2 WO 2005103110A2 US 2004039726 W US2004039726 W US 2004039726W WO 2005103110 A2 WO2005103110 A2 WO 2005103110A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyethylene terephthalate
- introducing
- ppm
- less
- terephthalate resin
- Prior art date
Links
- CYIDZMCFTVVTJO-UHFFFAOYSA-N OC(c(c(C(O)=O)c1)cc(C(O)=O)c1C(O)=O)=O Chemical compound OC(c(c(C(O)=O)c1)cc(C(O)=O)c1C(O)=O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
Definitions
- polyester containers, films, and fibers are an integral component in numerous consumer products manufactured worldwide.
- most commercial polyester used for polyester containers, films, and fibers is polyethylene terephthalate polyester.
- Polyester resins especially polyethylene terephthalate and its copolyesters, are also widely used to produce rigid packaging, such as two-liter soft drink containers.
- Polyester packages produced by stretch-blow molding possess outstanding strength and shatter resistance, and have excellent gas barrier and organoleptic properties as well. Consequently, such lightweight plastics have virtually replaced glass in packaging numerous consumer products (e.g., carbonated soft drinks, fruit juices, and peanut butter).
- modified polyethylene terephthalate resin is polymerized in the melt phase to an intrinsic viscosity of about 0.6 deciliters per gram (dl/g), whereupon it is further polymerized in the solid phase to achieve an intrinsic viscosity that better promotes bottle formation. Thereafter, the polyethylene terephthalate may be injection molded into preforms, which in turn may be blow molded into bottles.
- polyester resins cannot be efficiently formed into preforms and bottles that are suitable for hot-fill applications.
- Most high-clarity polyester bottles do not possess the necessary dimensional stability to be hot- filled with product at temperatures between about 180°F and 205°F, especially between about 195°F and 205°F.
- conventional polyester bottles exhibit unacceptable shrinkage and haze.
- Figures 1-2 illustrate differential scanning calorimetry thermal analyses performed on a titanium-catalyzed polyethylene terephthalate resin having an intrinsic viscosity of 0.78 dl/g and being modified with 1.6 mole percent diethylene glycol and 1.5 mole percent isophthalic acid.
- Figures 3-4 illustrate differential scanning calorimetry thermal analyses performed on an antimony-catalyzed polyethylene terephthalate resin having an intrinsic viscosity of 0.78 dl/g and being modified with 1.6 mole percent diethylene glycol and 1.5 mole percent isophthalic acid.
- Figures 5-6 illustrate differential scanning calorimetry thermal analyses performed on a titanium-catalyzed polyethylene terephthalate resin having an intrinsic viscosity of 0.78 dl/g and being modified with 1.6 mole percent diethylene glycol and 2.4 mole percent isophthalic acid.
- Figures 7-8 illustrate differential scanning calorimetry thermal analyses performed on an antimony-catalyzed polyethylene terephthalate resin having an intrinsic viscosity of 0.78 dl/g and being modified with 1.6 mole percent diethylene glycol and 2.4 mole percent isophthalic acid.
- Figure 9 illustrates percent haze versus preform thickness as measured in a step parison for titanium-catalyzed and antimony-catalyzed polyethylene terephthalate resins.
- Figure 10 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 11 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.
- Figures 12-13 illustrates the absorbance (cm "1 ) of a representative polyethylene terephthalate unenhanced by heat-up rate additives.
- the invention is a slow-crystallizing polyethylene terephthalate resin.
- the polyethylene terephthalate resins of the present invention possess a significantly higher heating crystallization exotherm peak temperature (T CH ) as compared with those of conventional antimony-catalyzed polyethylene terephthalate resins. This elevated heating crystallization exotherm temperature delays the onset of crystallization. Accordingly, the polyethylene terephthalate resins of the present invention are especially useful for making hot-fill bottles having exceptional clarity and shrinkage properties.
- the invention is a polyethylene terephthalate resin possessing a heating crystallization exotherm peak temperature (T CH ) of more than about 140°C, an absorbance (A) of at least about 0.18 cm “1 at an wavelength of 1100 nm or 1280 nm, and an L* value of more than about 70 as classified in the CIE L*a*b* color space.
- T CH heating crystallization exotherm peak temperature
- A absorbance
- L* value of more than about 70 as classified in the CIE L*a*b* color space.
- the invention is a polyethylene terephthalate resin that includes at least 2 parts per million (ppm) — and preferably less than 50 ppm — of elemental titanium and less than about 6 mole percent comonomer substitution.
- This titanium-catalyzed polyethylene terephthalate resin is especially useful in containers, films, and packaging, but may be used for fibers, yarns, and fabrics as well.
- the invention is a polyethylene terephthalate preform that is useful for enhanced heat-set bottles.
- the polyethylene terephthalate preform possesses a heating crystallization exotherm peak temperature (T CH ) of more than about 140°C, an absorbance (A) of at least about 0.18 cm “1 at an wavelength of 1100 nm or 1280 nm, and an L* value of more than about 70 as classified in the CIE L*a*b* color space.
- the invention is a polyester preform that can be formed into a high-clarity bottle that has excellent, low shrinkage properties.
- the preform includes less than about six (6) mole percent comonomer substitution and has an intrinsic viscosity of less than about 0.86 dl/g.
- the invention is a high-clarity, hot-fill bottle formed from the preform.
- the invention is a polyester preform that can be formed into a high-clarity bottle having excellent thermal expansion properties.
- the preform includes less than about 6 mole percent comonomer substitution and has an intrinsic viscosity of between about 0.78 and 0.86 dl/g.
- the invention is a high-clarity, carbonated soft drink bottle formed from the preform.
- the carbonated soft drink bottle is capable of withstanding internal pressures of about 60 psig.
- the invention is a titanium-based catalyst system that facilitates the melt phase polymerization of polyethylene terephthalate resins.
- the invention is a catalyst system of Group I and Group II metals that facilitates the solid state polymerization (SSP) of polyethylene terephthalate resins.
- SSP catalyst system preferably includes alkali earth metals (i.e., Group I metals), alkaline earth metals (i.e., Group II metals), or both.
- the invention embraces methods for making such polyester resins, preforms, and bottles.
- the method generally includes reacting a terephthalate component and a diol component (i.e., a terephthalate moiety and a diol moiety) in the presence of a titanium catalyst to form polyethylene terephthalate precursors, which are then polymerized via melt phase polycondensation to form polymers of polyethylene terephthalate of a desired molecular weight.
- a titanium catalyst to form polyethylene terephthalate precursors, which are then polymerized via melt phase polycondensation to form polymers of polyethylene terephthalate of a desired molecular weight.
- ethylene glycol is continuously removed to create favorable reaction kinetics.
- polyethylene terephthalate polymers are, in fact, modified polyethylene terephthalate polyesters.
- the polyethylene terephthalate resins described herein are preferably modified polyethylene terephthalate polyesters.
- the modifiers in the terephthalate component and the diol component are typically randomly substituted in the resulting polyester composition.
- the titanium-catalyzed polyethylene terephthalate resin possesses low comonomer substitution.
- the polyethylene terephthalate generally includes less than about 6 mole percent comonomer substitution.
- the polyethylene terephthalate typically includes less than 5 mole percent comonomer substitution or more than 2 mole percent comonomer substitution, or both.
- the polyethylene terephthalate preferably includes between about 3 and 4 mole percent comonomer substitution.
- the modified polyethylene terephthalate is composed of about a 1:1 molar ratio of (1) a diacid component of 2.4 mole percent isophthalic acid with the remainder terephthalic acid, and (2) a diol component of 1.6 mole percent diethylene glycol and the remainder ethylene glycol.
- diol component refers primarily to ethylene glycol, although other diols (e.g., diethylene glycol) may be used as well.
- terephthalate component broadly refers to diacids and diesters that can be used to prepare polyethylene terephthalate.
- the terephthalate component mostly includes either terephthalic acid or dimethyl terephthalate, but can include diacid and diester comonomers as well.
- the "terephthalate component” is either a “diacid component” or a "diester component.”
- diacid component refers somewhat more specifically to diacids (e.g., terephthalic acid) that can be used to prepare polyethylene terephthalate via direct esterification.
- diacid component is intended to embrace relatively minor amounts of diester comonomer (e.g., mostly terephthalic acid and one or more diacid modifiers, but optionally with some diester modifiers, too).
- diester component refers somewhat more specifically to diesters (e.g., dimethyl terephthalate) that can be used to prepare polyethylene terephthalate via ester exchange.
- diester component is intended to embrace relatively minor amounts of diacid comonomer (e.g., mostly dimethyl terephthalate and one or more diester modifiers, but optionally with some diacid modifiers, too).
- the term "comonomer” is intended to include monomeric and oligomeric modifiers (e.g., polyethylene glycol).
- the diol component can include other diols besides ethylene glycol (e.g., diethylene glycol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexane dimethanol, neopentyl glycol, and isosorbide), or the terephthalate component, in addition to terephthalic acid or its dialkyl ester (i.e., dimethyl terephthalate), can include modifiers such as isophthalic acid or its dialkyl ester (i.e., dimethyl isophthalate), 2,6-naphthalene dicarboxylic acid or its dialkyl ester (i.e., dimethyl 2,6 naphthalene dicarboxylate), adipic acid or its dialkyl ester (i.e., dimethyl adipate), succinic acid, its dialkyl ester (i.e., dimethyl succinate), or its anhydride (i
- isophthalic acid and diethylene glycol are the preferred modifiers.
- cyclohexane dimethanol efficiently suppresses polymer crystallinity, but has poor oxygen permeability properties.
- terephthalate fiber resins For polyethylene terephthalate fiber resins according to the present invention, no comonomer substitution is necessary, but where employed, preferably includes diethylene glycol or polyethylene glycol. [0044] It will be understood that diacid comonomer should be employed when the terephthalate component is mostly terephthalic acid (i.e., a diacid component), and diester comonomer should be employed when the terephthalate component is mostly dimethyl terephthalate (i.e., a diester component).
- diacid comonomer should be employed when the terephthalate component is mostly terephthalic acid (i.e., a diacid component)
- diester comonomer should be employed when the terephthalate component is mostly dimethyl terephthalate (i.e., a diester component).
- the molar ratio of the diacid component and the diol component is typically between about 1.0:1.0 and 1.0:1.6.
- the molar ratio of the diester component and the diol component is typically greater than about 1.0:2.0.
- the diol component usually forms the majority of terminal ends of the polymer chains and so is present in the resulting polyester composition in slightly greater fractions. This is what is meant by the phrases "about a 1:1 molar ratio of a terephthalate component and a diol component,” “about a 1:1 molar ratio of a diacid component and a diol component,” and “about a 1:1 molar ratio of the diester component and the diol component,” each of which may be used to describe the polyester compositions of the present invention.
- the titanium-catalyzed polyethylene terephthalate resin is preferably composed of about a 1:1 molar ratio of a diacid component and a diol component.
- the diacid component includes at least 94 mole percent terephthalic acid (e.g., terephthalic acid and isophthalic acid) and the diol component includes at least 94 mole percent ethylene glycol (e.g., ethylene glycol and diethylene glycol).
- the titanium-catalyzed polyethylene terephthalate resin according to the present invention generally possesses an intrinsic viscosity of less than about 0.86 dl/g. Those having ordinary skill in the art will appreciate, however, that during injection molding operations polyester resins tend to lose intrinsic viscosity (e.g., an intrinsic viscosity loss of about 0.02-0.06 dl/g from chip to preform).
- the polyethylene terephthalate generally has an intrinsic viscosity of less than about 0.86 dl g, such as between about 0.72 dl/g and 0.84 dl/g). More typically, the polyethylene terephthalate has an intrinsic viscosity of more than about 0.68 dl/g or less than about 0.80 dl/g, or both (i.e., between about 0.68 dl/g and 0.80 dl/g).
- the polyethylene terephthalate preferably has an intrinsic viscosity of more than about 0.72 dl/g or less than about 0.78 dl g, or both (i.e., between about 0.72 dl/g and 0.78 dl/g). Most preferably, the polyethylene terephthalate has an intrinsic viscosity of more than about 0.75 dl/g as well (i.e., between about 0.75 dl/g and 0.78 dl/g).
- heat-setting performance diminishes at higher intrinsic viscosity levels and mechanical properties (e.g., stress cracking, drop impact, and creep) decrease at lower intrinsic viscosity levels (e.g., less than 0.6 dl/g).
- the polyethylene terephthalate typically has an intrinsic viscosity of more than about 0.72 dl/g or less than about 0.84 dl/g, or both (i.e., between about 0.72 dl/g and 0.84 dl/g).
- the polyethylene terephthalate preferably has an intrinsic viscosity of more than about 0.78 dl/g, and most preferably, an intrinsic viscosity of between about 0.80 dl/g and 0.84 dl/g.
- the polyethylene terephthalate typically has an intrinsic viscosity of between about 0.50 dl/g and 0.70 dl/g and preferably an intrinsic viscosity between about 0.60 dl/g and 0.65 dl/g (e.g., 0.62 dl/g).
- the polyethylene terephthalate fiber resins are typically polymerized only in the melt phase (i.e., the fiber resins usually do not undergo solid state polymerization).
- 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, Fair-child'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.
- 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° and 25°C), and the relative viscosity is measured. As noted, intrinsic viscosity is calculated from relative viscosity.
- the titanium-catalyzed polyethylene terephthalate resin typically includes between about 2 ppm and 50 ppm of elemental titanium.
- the resin includes less than 25 ppm of elemental titanium (e.g., between about 2 and 20 ppm). More preferably, the resin includes at least about 5 ppm of elemental titanium or less than about 15 ppm of elemental titanium, or both (i.e., between about 5 and 15 ppm, such as about 10 ppm).
- the titanium catalyst is typically a titanate, such as titanium diisopropoxide bis(acetyl-acetonate) or tetrabutyl titanate.
- Germanium is an excellent polyethylene terephthalate catalyst. Germanium, however, is prohibitively expensive and so is disfavored in the production of commercial polyesters.
- the present resin reduces costs by including less than about 20 ppm of elemental germanium, typically less than about 15 ppm of elemental germanium, and more typically less than about 10 ppm of elemental germanium.
- the titanium- catalyzed polyethylene terephthalate resins include less than 5 ppm of elemental germanium and more preferably less than about 2 ppm of elemental germanium.
- the titanium-catalyzed polyethylene terephthalate resins are essentially free of elemental germanium. In other instances, however, the titanium-catalyzed polyethylene terephthalate resins include at least about two ppm of elemental germanium.
- titanium- catalyzed polyester resins possess lower rates of crystallization as compared with conventional antimony-catalyzed polyester resins.
- the titanium-catalyzed polyethylene terephthalate resins of the present invention thus possess lower crystallinity than otherwise identical antimony-catalyzed polyethylene terephthalate resins.
- titanium is a poor nucleator as compared with antimony. Consequently, the titanium-catalyzed polyethylene terephthalate resins of the present invention possess lower crystallization rates as compared with antimony-catalyzed polyesters. As will be understood by those having ordinary skill in art, this permits preforms according to the present invention to be blow molded into high-clarity bottles.
- the present resin includes less than about 100 ppm of elemental antimony, typically less than about 75 ppm of elemental antimony, and more typically less than about 50 ppm of elemental antimony.
- the titanium-catalyzed polyethylene terephthalate resins include less than 25 ppm of elemental antimony and more preferably less than about 10 ppm of elemental antimony.
- the titanium-catalyzed polyethylene terephthalate resins are essentially free of elemental antimony. Antimony-free polyethylene terephthalate resins may be desirable as antimony is considered a heavy metal. In other instances, however, the titanium-catalyzed polyethylene terephthalate resins include at least about 10 ppm of elemental antimony.
- Figures 1-8 depict differential scanning calorimetry (DSC) thermal analyses performed on both titanium-catalyzed and antimony-catalyzed polyester resins at an intrinsic viscosity of about 0.78 dl/g.
- Figures 1-4 compare titanium-catalyzed and antimony- catalyzed polyethylene terephthalate resins having about 3 mole percent comonomer substitution.
- Figures 5-8 compare the titanium-catalyzed and antimony-catalyzed polyethylene terephthalate resins including about 4 mole percent comonomer substitution.
- the differential scanning calorimetry was performed by (1) holding a modified polyethylene terephthalate sample for one minute at 30 degrees Celsius; (2) heating the sample from 30 degrees Celsius to 280 degrees Celsius at 10 degrees Celsius per minute; (3) holding the sample at 280 degrees Celsius for two minutes; and (4) cooling the sample from 280 degrees to 30 degrees Celsius at 10 degrees Celsius per minute.
- Figures 1, 3, 5, and 7 correspond to the heating of amorphous polymer and
- Figures 2, 4, 6, and 8 correspond to the cooling of the same polymer from the melt phase.
- FIGS 1-2 show that at the comonomer substitution of about 3 percent (i.e., 1.6 mole percent diethylene glycol and 1.5 mole percent isophthalic acid substitution), the titanium-catalyzed polyethylene terephthalate polyester possesses a heating crystallization exotherm peak temperature (T CH ) of 144.2°C, crystalline melting peak temperature (T M ) of 253.2°C, and a cooling crystallization exotherm peak temperature (Tec) of 186.8°C
- T CH heating crystallization exotherm peak temperature
- T M crystalline melting peak temperature
- Tec cooling crystallization exotherm peak temperature
- Figures 3-4 show that at the comonomer substitution of about 3 percent (i.
- antimony-catalyzed polyethylene terephthalate polyester possesses a heating crystallization exotherm peak temperature (T CH ) of 130.6°C, crystalline melting peak temperature (T ) of 251.5°C, and a cooling crystallization exotherm peak temperature (Tec) of 191.0°C.
- FIGS 5-6 show that at the comonomer substitution of about 4 percent (i.e., 1.6 mole percent diethylene glycol and 2.4 mole percent isophthalic acid substitution), the titanium-catalyzed polyethylene terephthalate polyester possesses a heating crystallization exotherm peak temperature (T CH ) of 146.3°C, crystalline melting peak temperature (T M ) of 250.0°C, and a cooling crystallization exotherm peak temperature (Tec) of 181.3°C.
- T CH heating crystallization exotherm peak temperature
- T M crystalline melting peak temperature
- Tec cooling crystallization exotherm peak temperature
- Figures 7-8 show that at the comonomer substitution of about 4 percent (i.e., 1.6 mole percent diethylene glycol and 2.4 mole percent isophthalic acid substitution), antimony-catalyzed polyethylene terephthalate polyester possesses a heating crystallization exotherm peak temperature(TcH) of 131.5°C, crystalline melting peak temperature (T M ) of 250.9°C, and a cooling crystallization exotherm peak temperature (Tec) of 187.8°C.
- TcH heating crystallization exotherm peak temperature
- T M crystalline melting peak temperature
- Tec cooling crystallization exotherm peak temperature
- the titanium-catalyzed polyethylene terephthalate resins of the present invention possess a significantly higher heating crystallization exotherm peak temperature (T CH ) as compared with antimony-catalyzed polyethylene terephthalate.
- T CH heating crystallization exotherm peak temperature
- Those having ordinary skill in the art will appreciate that this higher heating crystallization exotherm temperature is especially desirable in blow molding operations as it delays the onset of crystallization, thereby facilitating the formation of high-clarity bottles.
- the polyethylene terephthalate resin has a heating crystallization exotherm peak temperature (T CH ) of more than about 140°C and preferably more than about 142°C (e.g., between 143°C and 153°C).
- T CH heating crystallization exotherm peak temperature
- the polyethylene terephthalate resin can possess a crystallization exotherm peak temperature (T CH ) of 155°C or more.
- T CH heating crystallization exotherm peak temperature
- the polyethylene terephthalate resin also has a crystalline melting peak temperature (T M ) of at least about 240°C, typically at least about 245°C, and more typically at least about 250°C.
- T M crystalline melting peak temperature
- the polyethylene terephthalate resin has a cooling crystallization exotherm peak temperature (Tec) of less than about 190°C and typically less than about 185°C. In some instances, the polyethylene terephthalate resin has a cooling crystallization exotherm peak temperature (Tec) of less than about 180°C.
- the titanium-catalyzed polyethylene terephthalate resin of the present invention possesses high clarity as compared with an otherwise identical antimony-catalyzed polyethylene terephthalate resin.
- Figure 9 depicts percent haze versus preform thickness as measured in a step parison for titanium-catalyzed and antimony- catalyzed polyethylene terephthalate resins at an intrinsic viscosity of about 0.78 dl/g and either 3 mole percent comonomer substitution (i.e., 1.6 mole percent diethylene glycol and 1.5 mole percent isophthalic acid substitution) or 4 mole percent comonomer substitution (i.e., 1.6 mole percent diethylene glycol and 2.4 mole percent isophthalic acid substitution).
- 3 mole percent comonomer substitution i.e., 1.6 mole percent diethylene glycol and 1.5 mole percent isophthalic acid substitution
- 4 mole percent comonomer substitution i.e., 1.6 mole percent di
- Figure 9 illustrates that at a given comonomer substitution, the titanium-catalyzed polyethylene terephthalate resin possesses substantially lower haze as compared with its corresponding antimony-catalyzed polyethylene terephthalate resin.
- the polyethylene terephthalate of the present invention typically possesses less than about 20 percent haze — preferably less than about 15 percent haze— at a thickness of more than about 6 mm and less than about 5 percent haze at a thickness of more than about 4 mm.
- the polyethylene terephthalate preferably possesses less than about 10 percent haze at a thickness of more than about 4.5 mm, and sometimes at a thickness of more than 5.5 mm (e.g., less than about 10 percent haze at a thickness of between 4.5 and 6.0 mm).
- the polyethylene terephthalate possesses less than about 20 percent haze at a thickness of between 5.5 and 6.5 mm as measured in a step parison. As depicted in Figure 9, the polyethylene terephthalate can possess less than about 50 percent haze at a thickness of more than about 7 mm.
- polyethylene terephthalate preforms and bottles must possess excellent color (i.e., not too yellow). In this regard, excessive levels of titanium catalyst can cause the polyethylene terephthalate resin to appear yellow.
- L*a*b* color space of the Commission Internationale l'Eclairage (CIE).
- CIE Commission Internationale l'Eclairage
- L* which describes luminosity on a scale of 0-100 (i.e., 0 is black and 100 is white)
- a* which describes the red-green axis (i.e., positive values are red and negative values are green)
- b* which describes the yellow-blue axis (i.e., positive values are yellow and negative values are blue).
- L* and b* values are of particular interest.
- polyester color be measured after polymerization in the solid phase.
- the polyethylene terephthalate resin of the present invention possesses an L* value (i.e., luminosity) of more than about 70, preferably more than about 75 (e.g., 77), and most preferably more than about 80 as classified in the CIE L*a*b* color space.
- the polyethylene terephthalate resin preferably possesses a b* color value of less than about 2 — more preferably less than about 0 — as classified by the CIE L*a*b* color space.
- the polyethylene terephthalate resin possesses a b* color value of between about -3 and 2 as classified by the CIE L*a*b* color space.
- polyethylene terephthalate resins are typically formed into pellets before undergoing crystallization and solid state polymerization.
- the polyethylene terephthalate resins of the present invention are crystalline pellets; it is preferred that color be measured in that form.
- the CIE L*a*b* color space values reported herein for the polyethylene terephthalate resins of the present invention relate to crystalline polyethylene terephthalate pellets.
- CIE L*a*b* color space values for the crystalline polyethylene terephthalate pellets were determined using a HunterLab LabScan XE spectrophotometer (illuminant/ observer: D65/10°; 45 0° geometry; perfect reflectance diffuser NBS78; standard color tile LX16697).
- crystalline polyester pellets are translucent and so are typically measured via reflectance using a clear sample cup.
- test procedures e.g., standards and calibrations
- appropriate for measuring color properties of crystalline polyester in various forms are readily available to and within the understanding of those having ordinary skill in the art. See http://www.hunterlab.com/measurementmethods.
- the polyethylene terephthalate resin of the present invention can be injection molded into preforms, which in turn may be blow molded into bottles. Measuring color in preforms and bottles, however, can be awkward. Consequently, it is preferred that preforms and bottles be formed into plaques to facilitate comparative color measurements.
- the polyethylene terephthalate preforms and bottles according to the present invention are ground, melted at 280°C, and then injected into a cold mold to form standard, three millimeter (3 mm) non-crystalline polyester test plaques.
- the CIE L*a*b* color space values reported herein for the polyethylene terephthalate preforms and bottles of the present invention relate to measurements taken upon such standard test plaques.
- the polyethylene terephthalate preforms and bottles of the present invention preferably possess a b* color value of less than about 4 — more preferably less than about 2 (e.g., less than about 0) — as classified by the CIE L*a*b* color space.
- the polyethylene terephthalate preforms and bottles possess a b* color value of between about -3 and 3 as classified by the CIE L*a*b* color space.
- the polyethylene terephthalate preforms and bottles of the present invention possess an L* value of more than about 70, preferably more than about 75 (e.g., 77), and most preferably more than about 80 (e.g., 83 or more) as classified in the CIE L*a*b* color space.
- CIE L*a*b* color space values refer to measurements from standard, non-crystalline polyester test plaques.
- CIE L*a*b* color space values for the three-millimeter, non-crystalline polyethylene terephthalate test plaques were determined using a HunterLab Lab Scan XE spectrophotometer (illuminant/ observer: D65/10 0 ; diffuse 8° standard; transmittance port).
- Those having ordinary skill in the art will appreciate that non-crystalline polyester plaques are essentially transparent and so are measured by transmittance.
- test procedures e.g., standards and calibrations
- appropriate for measuring color properties of non-crystalline polyester in various forms are readily available to and within the understanding of those having ordinary skill in the art. See http://www.hunterlab.com/measurementmethods.
- Such color has been achieved according to the present invention by including between about 10 and 50 ppm of elemental cobalt, preferably between about 15 and 40 ppm of elemental cobalt, and most preferably between 20 and 30 ppm of elemental cobalt.
- the polyethylene terephthalate resin of the present invention tends to appear yellowish.
- the present polyethylene terephthalate resin possesses excellent color without the inclusion of colorants, apart from a cobalt catalyst. (Those having ordinary skill in the art will appreciate that cobalt not only provides catalytic activity, but also imparts blue coloration to the polyethylene terephthalate resin.)
- the polyethylene terephthalate resin is intended for packaging (e.g., polyester preforms and bottles), it preferably includes a heat-up rate additive.
- the heat-up rate additive is present in the resin in an amount sufficient to improve the resin's reheating profile.
- a heat-up rate additive helps preforms absorb energy during preform reheating processes. In reheating preforms, the inside of the preform should be at least as warm as the outside of the preform as the inside undergoes more stretching during blow molding.
- U.S. Patent No. 6,699,546 (Tseng) teaches the inclusion of nucleation agents to accelerate the rate of resin crystallization for improved heat-set bottles.
- slow-crystallizing polyethylene terephthalate resins possess a significantly higher heating crystallization exotherm peak temperature (T CH ) as compared with those of antimony-catalyzed polyethylene terephthalate resins.
- T CH heating crystallization exotherm peak temperature
- the objective of the heat-setting process is to maximize bottle crystallinity and stress relaxation while maintaining clarity. It would seem that a slower crystallizing resin would have inferior heat- setting capability. Consequently, including a heat-up rate additive to achieve higher preform temperatures — and thus promoting crystallinity in the slower crystallizing resin — would seem to be of no practical benefit. Under such circumstances, those having ordinary skill in the art would not expect to achieve improved bottle properties (e.g., clarity and shrinkage).
- a bottle preform made from a slow-crystallizing polyethylene terephthalate resin (e.g., the titanium-catalyzed polyester resins herein disclosed) that further includes a heat-up rate additive.
- a slow-crystallizing polyethylene terephthalate resin e.g., the titanium-catalyzed polyester resins herein disclosed
- titanium slows the onset of thermal crystallization in the preform as the preform is heated.
- the heat-up rate additive causes the preform to absorb more energy and, therefore, to reach significantly higher temperatures before the onset of crystallization. Thus, good preform clarity is maintained even at elevated preform temperatures.
- modifying a slow-crystallizing polyester resin to include sufficient heat-up rate additive to enhance the resin's reheating profile actual improves blow molding performance and bottle properties, such as shrinkage.
- the increased preform temperature in the blow molding and heat-setting processes promotes bottle crystallization and stress relaxation while producing bottles having clarity superior to those of antimony-catalyzed polyethylene terephthalate resins.
- the heat-up rate additive is a carbon-based heat-up rate additive.
- Carbon-based heat-up rate additive is typically present in the polyethylene terephthalate resin in an amount less than about 25 ppm. More preferably, carbon-based heat-up rate additive is present in the polyethylene terephthalate resin in an amount between about 4 and 16 ppm (e.g., 8-12 ppm), most preferably in an amount between about 6 and 10 ppm.
- Suitable carbon-based additives include carbon black, activated carbon, and graphite. For example, satisfactory carbon black heat-up rate additives are disclosed in U.S. Patent No. 4,408,004 (Pengilly), which is hereby incorporated entirely by reference.
- the heat-up rate additive is a metal-containing heat-up rate additive.
- Metal-containing heat-up rate additive is typically present in the polyethylene terephthalate resin in an amount between about 10 and 300 ppm, more typically in an amount greater than about 75 ppm (e.g., between about 150 and 250 ppm).
- Suitable metal containing heat-up rate additives include metals, metal oxides, minerals (e.g., copper chromite spinels), and dyes.
- satisfactory inorganic black pigments and particles are disclosed in U.S. Patent No. 6,503,586 (Wu), which is hereby incorporated entirely by reference.
- Preferred metal-containing heat-up rate additives are tungsten-based additives, such as tungsten metal or tungsten carbide.
- tungsten-containing heat-up rate additive powders preferably have an average particle size of between about 0.7 and 5.0, microns, more preferably between about 0.9 and 2.0 microns.
- particle size is typically measured by techniques based on light scattering. Particle sizes and distributions are often characterized according to ASTM B330-2 ("Standard Test Method for Fisher Number of Metal Powders and Related Compounds").
- molybdenum-based • additives especially molybdenum sulfide (MoS 2 ).
- MoS 2 molybdenum sulfide
- molybdenum sulfide has outstanding heat absorption properties, so it can be included in somewhat lesser quantities (e.g., 5-100 ppm) as compared with other metal-containing heat-up rate additives.
- the most preferred heat-up rate additives are natural spinels and synthetic spinels.
- Spinels are preferably included in the polyethylene terephthalate resin in an amount between about 10 and 100 ppm (e.g., between about 15 and 25 ppm).
- Particularly outstanding spinel pigments are copper chromite black spinel and chrome iron nickel black spinel.
- the heat-up rate of a polyethylene terephthalate prefo ⁇ n can be described by surface temperature measurements at a fixed location on a preform for a particular bottle production rate.
- polyethylene terephthalate bottle preforms are reheated by passing the preforms through a reheat oven of a blow molding machine.
- the reheat oven consists of a bank of quartz lamps (3,000 and 2,500 watt lamps) that emit radiation mostly in the infrared range.
- quartz lamps 3,000 and 2,500 watt lamps
- Important bottle properties for bottle performance are material distribution, orientation, and sidewall crystallinity.
- Preform reheat temperature is important for control of these properties.
- the preform reheat temperature is typically in the range of 30-50°C above the glass transition temperature (T g ) of polyethylene terephthalate.
- T g glass transition temperature
- the reheat temperature depends on the application (e.g., hot-filled beverage bottle or carbonated soft drink bottles).
- the rate at which a preform can be reheated to the orientation temperature is important for optimal bottle performance in high-speed, polyethylene terephthalate blow-molding machines, such as those manufactured by Sidel, Inc. (LeHavre, France). This is especially true for heat-set bottles that are intended for filling with hot liquids in excess of 185°F.
- the preform In heat-set bottle production, the preform is reheated rapidly to as high a temperature as possible. This maximizes crystallization upon blow molding and avoids thermal crystallization in the preform. Those having ordinary skill in the art will appreciate that such thermal crystallization can cause unacceptable haze as a result of spherulitic crystallization.
- this test method analyzes the reheat characteristics of polyethylene terephthalate preforms (or resins) by forming test parisons from one or more polyethylene terephthalate resin formulations. It is the test parisons — not commercial preforms — that are actually tested:
- the subject resin is formed into a 5.25-inch test parison having a weight of 47 grams, an overall diameter of 1.125 inches, and a 0.75-inch neck finish.
- a polyethylene terephthalate resin is dried at 350°F for four hours in a desiccant dryer.
- the dried resin is introduced into a 4-ounce Newbury injection-molding machine.
- the resin is kneaded and melted to provide a molten resin with a temperature in the range of 500°F to 520°F.
- the molten resin is injected into a preform mold designed for a two- liter carbonated soft drink bottle.
- the total cycle time is 60 seconds, including injection, pack, and cooling time.
- the mold is continuously chilled to 45°F.
- the reheat performance of the 5.25-inch test parison is tested using a Sidel SBO1 laboratory blow molding machine.
- This machine has one reheat oven with a bank of up to ten independently adjustable quartz lamps, an infrared camera to measure preform surface temperature, a transfer arm form the oven to blow mold, one blow mold, and a bottle transfer arm extending from the blow mold to the machine exit.
- the SBO1 laboratory blow molding machine continuously produces polyethylene terephthalate bottles at a rate of 1,000 bottles per hour using eight quartz lamps.
- the oven has power control that can be adjusted as a percentage of the overall oven power output.
- each lamp can be adjusted as a percentage of the individual lamp power output.
- the machine is set up at a bottle production rate of 1,000 bottles per hour.
- a standard resin is selected to produce a test parison.
- the reheating profile for this test parison is established.
- the reheating profile is used to produce commercially acceptable bottles at an overall power output of 80 percent.
- the percentage of the overall power is varied between 65 and 90 percent and the surface temperature is repeatedly measured at a fixed location on the test parison.
- the reheat performance of the 5.25-inch test parison is consistently measured 1.4- inches below the support ring of the neck finish. At this location, (i.e., 1.4 inches below the support ring), the test parison has a wall thickness of 0.157-inch.
- a two-liter polyethylene terephthalate bottle test parison was produced from a standard resin (i.e., Wellman's PermaClear ® HP806 polyester resin). This test parison required eight reheat zones for production of a straight-wall, two-liter bottle. At an overall oven power percentage of 80 percent, the reheating profile for this PermaClear ® HP806 test parison is shown in Table 1 :
- Table 2 demonstrates that improved prefo ⁇ n reheat performance is achieved as a result of the inclusion of a heat-up rate additive.
- the polyethylene terephthalate resin of the present invention preferably includes a heat-up rate additive in a concentration sufficient for an aforementioned 5.25-inch test parison to achieve reheating surface temperatures that, as measured 1.4 inches below the support ring of the neck finish where the wall thickness is 0.157 inch, are at least about 4°C higher than corresponding reheating temperatures achievable by an otherwise identical 5.25-inch test parison (i.e., without a heat-up rate additive) as measured on a Sidel SBOl laboratory blow-molding machine operating at a production rate of 1,000 bottles per hour and using eight lamps at overall power levels of 65 percent, 70 percent, 75 percent, 80 percent, 85 percent, and 90 percent, respectively.
- the difference in respective reheating surface temperatures is more preferably at least about 7°C and most preferably at least about 10°C.
- the polyethylene terephthalate resin of the present invention preferably includes a heat-up rate additive in a concentration sufficient for an aforementioned 5.25-inch test parison to achieve an average reheating surface temperature that, as measured 1.4 inches below the support ring of the neck finish where the wall thickness is 0.157 inch, is at least about 5°C higher — preferably 10°C higher — than the average reheating temperature achievable by an otherwise identical 5.25-inch test parison (i.e., without a heat-up rate additive) as measured on a Sidel SBOl laboratory blow-molding machine operating at a production rate of 1,000 bottles per hour and using eight lamps at overall power levels between about 65 and 90 percent.
- a heat-up rate additive in a concentration sufficient for an aforementioned 5.25-inch test parison to achieve an average reheating surface temperature that, as measured 1.4 inches below the support ring of the neck finish where the wall thickness is 0.157 inch, is at least about 5°C higher — preferably 10°C higher — than the average
- the intrinsic heat-up rate of polyester resin can be described by its characteristic absorption of energy.
- electromagnetic radiation exists across several spectra.
- electromagnetic radiation can be measured in the ultraviolet, visible, near-infrared, and infrared ranges.
- the visible light spectrum falls between about 430 nm and 690 nm. This spectrum is bounded by ultraviolet radiation and infrared radiation, respectively.
- NIR near infrared radiation
- the intrinsic heat-up rate of polyester resin can be characterized by its absorbance of electromagnetic radiation. Absorbance is described by Beer's Law, which is expressed as equation 1 :
- A absorbance of electromagnetic radiation by a sample
- ⁇ is the proportionality constant of the sample (i.e., "molar absorptivity")
- / is the path length of the sample through which electromagnetic radiation must pass
- c is the concentration of the sample (typically measured in moles/liter).
- absorbance (A) can be calculated from transmittance (T) as follows:
- Equation 2 is further simplified as expressed in equation 3:
- transmittance is the ratio of the intensity of the electromagnetic radiation that passes through the polymer resin to the intensity of the electromagnetic radiation that enters the polymer resin.
- absorbance which is calculated from the relationship expressed in equation 3, describes the electromagnetic radiation that a non- crystalline polyethylene terephthalate resin fails to transmit.
- the polyethylene terephthalate resins of the present invention generally possess absorbance (A) of at least about 0.18 cm “1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.
- the present polyethylene terephthalate resins typically possess absorbance (A) of at least about 0.20 cm "1 at a wavelength of 1100 nm or at a wavelength of 1280 nm, preferably possess absorbance (A) of at least about 0.24 cm- 1 at a wavelength of 1100 nm or at a wavelength of 1280 nm absorbance (A), and more preferably possess absorbance (A) of at least about 0.28 cm "1 at a wavelength of 1100 nm or at a wavelength of 1280 nm absorbance (A).
- disjunctive i.e., "or”
- conjunctive i.e., "and”
- absorbance is reported for non-crystalline polyester.
- the polyethylene terephthalate resins possess an absorbance (A) of at least about 0.25 cm “1 at a wavelength of 1100 nm or at a wavelength of 1280 nm, and preferably an absorbance (A) of at least about 0.30 cm "1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.
- the polyethylene terephthalate resins possess an absorbance (A) of at least about 0.30 cm “1 at a wavelength of 1100 nm or at a wavelength of 1280 nm, and in particular embodiments an absorbance (A) of at least about 0.40 cm “1 at a wavelength of 1100 nm or at a wavelength of 1280 nm.
- These polyethylene terephthalate resins can be achieved by including between about 10 and 100 ppm of a copper chromite black spinel.
- absorbance was determined within the visible and NIR spectra for both a non-crystalline unenhanced polyethylene terephthalate resin (PET) and an otherwise identical polyethylene terephthalate resin, albeit enhanced with 22 ppm of a copper chromite black spinel heat-up rate additive (PET/spinel).
- PET polyethylene terephthalate resin
- PET/spinel copper chromite black spinel heat-up rate additive
- the wavelengths reported in Table 3 are meaningful. In particular, 550 nm falls near the midpoint of the visible light spectrum and 700 nm falls near the upper end of the visible spectrum. Moreover, as depicted in Figures 12-13, the absorbance for unenhanced polyethylene terephthalate is nearly flat (i.e., the slope is about 0) at 1100 nm and 1280 nm, thereby facilitating repeatable measurements at these wavelengths within the NIR spectrum.
- heat-up rate additives promote the absorption of more NIR radiation and lesser amounts of visible radiation. This can be described by the absorption ratio as herein defined. In brief, for a polyester resin, the absorption ratio is simply the antilog of the absorbance at a first wavelength divided by the antilog of the absorbance at a second wavelength. This is expressed in equation 4:
- Ai is absorbance at a first wavelength
- a 2 is absorbance at a second wavelength.
- the first wavelength typically falls within the NIR spectrum (e.g., 1280 nm) and the second wavelength typically falls within the visible spectrum (e.g., 550 nm).
- Table 4 indicates that the polyethylene terephthalate enhanced with 22 ppm of copper chromite spinel has similar absorption selectivity to that of the unenhanced polyethylene terephthalate, despite having significantly higher absorbance (e.g., absorbance greater than 0.30 cm "1 at both 1100 nm and 1280 nm).
- the present polyethylene terephthalate resins preferably possess a 1100:550 absorption ratio of at least about 70 percent or a 1280:550 absorption ratio of at least about 70 percent. More preferably, the present polyethylene terephthalate resins possess a 1100:550 absorption ratio of at least about 75 percent or a 1280:550 absorption ratio of at least about 75 percent. In some embodiments, the present polyethylene terephthalate resins preferably possess a 1100:550 absorption ratio of at least about 80 percent or a 1280:550 absorption ratio of at least about 80 percent.
- the present polyethylene terephthalate resins preferably possess a 1100:700 absorption ratio of at least about 85 percent or a 1280:700 absorption ratio of at least about 85 percent. In some embodiments, the present polyethylene terephthalate resins possess a 1100:700 absorption ratio of at least about 90 percent (e.g., 95 percent or more) or a 1280:700 absorption ratio of at least about 90 percent (e.g., 95 percent or more).
- absorbance was determined for three _ millimeter (3 mm), non-crystalline polyester plaques using a Foss Series 6500 Transport Analyzer.
- This instrument is typical of those capable of measuring transmittance in the visible and NIR spectra in that instrumentation factors (e.g., lamp, detector, vibration, and air filtration) can affect absorbance measurements.
- instrumentation factors e.g., lamp, detector, vibration, and air filtration
- the absorbance data must be normalized at an incident wavelength of 2132 nm such that the corresponding absorbance is 0.473 mm “1 (i.e., 4.73 cm “1 ). At this wavelength additives have modest effect on absorbance for non- crystalline polyethylene terephthalate.
- reflectance is radiation that has been scattered from the surface of a solid, liquid, or gas. Reflected electromagnetic energy is expressed in relation to the energy absorbed and energy transmitted as expressed in equation 5:
- I A is absorbed energy
- I R is reflected energy
- absorbance is derived from the transmittance. See equation 3. Reflectance is generally not measured, and so the inventors have considered whether ignoring reflectance introduces substantial errors in the determination of absorbance.
- the polyester plaques should have a consistent finish across batches (i.e., semi-glossy). It is believed that by controlling the physical properties of the polyester plaques in this way, reflectance becomes negligible in assessing absorbance and absorption ratio.
- 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 monomers and oligomers are subsequently catalytically polymerized via polycondensation to form polyethylene terephthalate polyester.
- ethylene glycol is continuously removed during polycondensation to create favorable reaction kinetics.
- 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, catalyzed ester exchange reaction (i.e., transesterification) to form bis(2-hydroxyethyl)-terephthalate monomers, as well as methanol as a byproduct.
- the methanol must be continuously removed as it is formed.
- the bis(2- hydroxyethyl)terephthalate monomer product is then catalytically polymerized via polycondensation to produce polyethylene terephthalate polymers.
- the resulting polyethylene terephthalate polymers are substantially identical to the polyethylene terephthalate polymer resulting from direct esterification using terephthalic acid, albeit with some minor chemical differences (e.g., 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 direct esterification reaction is preferred over the older, two-step ester exchange reaction, which is less economical and which often yields polyethylene terephthalate resins having poor color.
- the direct esterification technique reacts terephthalic acid and ethylene glycol along with no more than 6 mole percent diacid and diol modifiers to form low molecular weight monomers, oligomers, and water.
- both titanium and cobalt catalysts preferably are added during esterification as this has been found to improve the color of the resulting polyethylene terephthalate resins.
- the polyethylene terephthalate resin may optionally include other catalysts, such as aluminum-based catalysts, manganese-based catalysts, or zinc-based catalysts.
- the titanium catalyst is introduced in an amount sufficient for the final polyethylene terephthalate resin to include between about 2 and 50 ppm of elemental titanium.
- the cobalt catalyst is introduced in an amount sufficient for the final polyethylene terephthalate resin to include between about 10 and 50 ppm of elemental cobalt.
- process disruptions e.g., clogged piping
- a titanium or cobalt catalyst increases the rate of esterification and polycondensation and, hence, the production of the polyethylene terephthalate resins.
- These catalysts will eventually degrade the polyethylene terephthalate polymer.
- degradation may include polymer discoloration (e.g., yellowing), acetaldehyde formation, or molecular weight reduction.
- stabilizing compounds can be employed to sequester ("cool") the catalysts.
- the most commonly used stabilizers contain phosphorus, typically in the form of phosphates and phosphites.
- the present resin typically includes a phosphorus stabilizer.
- the phosphorus stabilizer is preferably introduced into the polyethylene terephthalate polymers such that the phosphorus is present in the resulting resin, on an elemental basis, in an amount less than about 60 ppm, typically between about 2 and 40 ppm, preferably in an amount less than about 15 ppm (e.g., between about 5 and 15 ppm), and more preferably in an amount less than about 10 ppm (i.e., between about 2 and 10 ppm).
- the phosphorus stabilizer may be introduced into the melt phase any time after esterification, but it is preferred that the phosphorus stabilizer be added to the melt after polycondensation is essentially complete.
- thermal stability refers to a low rate of acetaldehyde generation, low discoloration, and retention of molecular weight following subsequent heat treatment or other processing.
- the phosphorus stabilizer may provide insufficient opportunity for the stabilizer to fully blend with the polymer. Consequently, the phosphorus stabilizer may not prevent degradation and discoloration of the polyester. In addition, adding phosphorus stabilizer during polymer processing is often inconvenient and does not provide economies of scale.
- U.S. Patent No. 5,376,702 for a Process and Apparatus for the Direct and Continuous Modification 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 phosphorus, 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. 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.
- the phosphorus stabilizers herein disclosed can be introduced to the polyethylene terephthalate polymers directly, as a concentrate in polyethylene terephthalate, or as a concentrate in a liquid carrier.
- the preferred point of addition in the polyethylene terephthalate polymerization process is after completion of polycondensation (i.e., mixed with the molten polymer stream after the final polymerization vessel).
- the phosphorus stabilizer is preferably introduced to the polyethylene terephthalate polymers via a reactive carrier, rather than via an inert carrier or no carrier at all.
- the reactive carrier which preferably has a molecular weight of more than about 200 g/mol and less than about 10,000 g/mol may be introduced during polycondensation, or more preferably, after the polycondensation is complete. In either respect, the reactive carrier should be introduced to the polyethylene terephthalate polymers in quantities such that bulk polymer properties are not significantly affected.
- the reactive carrier should make up no more than about one weight percent of the polyethylene terephthalate resin.
- the reactive carrier is introduced to the polyethylene terephthalate polymers in quantities such that its concentration in the polymer resin is less than about 1,000 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.
- the reactive carrier has a melting point that ensures that it is a liquid or slurry at near ambient temperatures.
- Near ambient temperatures not only simplify the unit operations (e.g., extruders, heaters, and piping), but also minimize degradation of the inert particulate additives.
- near ambient includes temperatures between about 20°C and 60°C.
- reactive carriers having carboxyl, hydroxyl, or amine functional groups are favored.
- Polyethylene glycol is a preferred polyol.
- polystyrene resin examples include functional polyethers, such as polypropylene glycol that is prepared from propylene oxide, random and block copolymers of ethylene oxide and propylene oxide, and polytetrame thylene glycol that is derived from the polymerization of tetrahydrofuran.
- functional polyethers such as polypropylene glycol that is prepared from propylene oxide, random and block copolymers of ethylene oxide and propylene oxide, and polytetrame thylene glycol that is derived from the polymerization of tetrahydrofuran.
- the reactive carrier may 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 polyethylene terephthalate polymers.
- the reactive carrier may include non-functional esters, amides, or anhydrides that is capable of reacting into the polyethylene terephthalate polymers during solid state polymerization and that will not cause the polyethylene terephthalate polymers to suffer intrinsic viscosity loss during injection molding processes.
- a preferred method of making the titanium-catalyzed polyethylene terephthalate resin of the present invention includes reacting, in a heated esterification reaction, a diacid component that includes at least 94 mole percent terephthalic acid and a diol component that includes at least 94 mole percent ethylene glycol.
- the diacid and diol modifiers should be included such that the resulting polyethylene terephthalate polymer has less than about 6 mole percent comonomer substitution.
- the diacid component preferably includes between about 1.6 and 2.4 mole percent isophthalic acid with the remainder terephthalic acid, and the diol component of includes 1.6 mole percent diethylene glycol and the remainder ethylene glycol.
- the esterification reaction is catalyzed by both titanium and cobalt to form monomers and oligomers of terephthalic acid and diacid modifiers, and ethylene glycol and diol modifiers, as well as water, which is continuously removed as it is formed to enable the esterification reaction to go essentially to completion.
- the titanium catalyst and the cobalt catalyst are concurrently introduced in amounts sufficient for the polyethylene terephthalate resin to include between about 2 and 50 ppm (e.g., 5-15 ppm) of elemental titanium and between about 10 and 50 ppm of elemental cobalt (e.g., 20-30 ppm).
- the monomers and oligomers are then polymerized via melt phase polycondensation to form polyethylene terephthalate polymers.
- a phosphorus stabilizer is then introduced into the polyethylene terephthalate polymers, preferably using a reactive carrier. As noted, the reactive carrier facilitates uniform blending within the polymer melt.
- the phosphorus stabilizer is typically introduced into the polyethylene terephthalate polymers such that the phosphorus is present in the resulting resin, on an elemental basis, in an amount between about 2 and 60 ppm — preferably less than about 10 or 15 ppm.
- polyethylene terephthalate polymers are formed into pellets, which are then polymerized in the solid state to an intrinsic viscosity of less than 0.86 dl/g (e.g., 0.75 - 0.78 dl/g).
- 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 (e.g., 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 (e.g., quantities such that its concentration in the polymers is less than about one weight percent).
- the polyethylene terephthalate polymers are then formed into chips (or pellets via a polymer cutter) before being solid state polymerized.
- the polyol reactive carrier combines with the polyethylene terephthalate polymer such that it is non-extractable during subsequent processing operations (e.g., forming polyester preforms or beverage containers).
- additives can be incorporated via reactive carrier into the polyethylene terephthalate resins of the present invention.
- additives include preform heat-up rate enhancers, friction-reducing additives, UV absorbers, 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, UV absorbers, 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, acetaldeh
- 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.
- late addition via reactive carrier significantly reduces the time additives are exposed to high polycondensation temperatures.
- macromolecules are considered to be polymers at an intrinsic viscosity of about 0.45 dl/g. This roughly translates to a molecular weight of at least about 13,000 g/mol.
- the reactive carriers according to the present invention have molecular weights that are more than about 200 g/mol and less than about 10,000 g/mol.
- the molecular weight of the reactive carrier is typically less than 6,000 g/mol, preferably less than 4,000 g/mol, more preferably between about 300 and 2,000 g/mol, and most preferably between about 400 and 1,000 g/mol.
- molecular weight refers to number-average molecular weight, rather than weight-average molecular weight.
- Figures 10 and 11 illustrate the theoretical loss of intrinsic viscosity as a function of reactive carrier concentration at several molecular weights.
- Figure 10 depicts the impact of the reactive carrier on upon polyethylene terephthalate having an intrinsic viscosity of 0.63 dl/g.
- Figure 11 depicts the impact of the reactive carrier on upon polyethylene terephthalate having intrinsic viscosity of 0.45 dl/g. Note that at any concentration, the reactive carriers having higher molecular weights have less adverse effect upon intrinsic viscosity of the polymer resin.
- the continuous feed enters the 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 esterification reaction which is preferably catalyzed using both titanium and cobalt catalysts, forms low molecular weight monomers, oligomers, and water. The water is removed as the reaction proceeds to drive favorable reaction equilibrium.
- 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.
- 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 is operated at a pressure of between about 0 and 40 torr.
- each of the polymerization vessels is connected to a vacuum system having a condenser, 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.
- the polymer melt exits the polycondensation stage, typically from the high polymerizer, phosphorus stabilizer is introduced via a reactive carrier. Thereafter, the polymer melt is generally filtered and extruded. After extrusion, the polyethylene terephthalate is quenched, preferably by spraying with water, to solidify it. The solidified polyethylene terephthalate polyester is cut into chips or pellets for storage and handling purposes. The polyester pellets preferably have an average mass of about 15-20 mg. As used herein, the term "pellets" is used generally to refer to chips, pellets, and the like.
- the pellets formed from the polyethylene terephthalate polymers may be subjected to crystallization followed by solid state polymerization to increase the molecular weight of the polyethylene terephthalate resin.
- titanium is substantially less active as an SSP catalyst.
- complementary SSP catalysts are introduced to the polymer melt prior to solid phase polymerization, preferably during polycondensation.
- Preferred SSP catalysts include Group I and Group II metals.
- Acetate salts of Group I and Group II metals e.g., calcium acetate, lithium acetate, manganese acetate, potassium acetate, or sodium acetate
- terephthalate salts can increase solid state polymerization rates.
- the SSP catalyst is typically introduced in an amount sufficient for the final polyethylene terephthalate resin to include between about 10 and 70 ppm of the elemental metal.
- bottles formed from the resins and preforms described herein preferably have sidewall haze of less than about 15 percent, more preferably less than about 10 percent.
- a hot-fill bottle according to the present invention exhibits an average circumferential dimension change, as measured from the bottle shoulder to the bottle base, of less than about 3 percent when filled at 195°F and less than about 5 percent when filled at 205°F. Moreover, such a hot-fill bottle according to the present invention exhibits a maximum circumferential dimension change from the bottle shoulder to the bottle base of less than about 5 percent — preferably less than 4 percent — when the bottle is filled at 195°F. (Such shrinkage properties are measured on a 24-hour aged bottle.)
- polyethylene terephthalate is typically converted into a container via a two-step process.
- an amorphous bottle preform e.g., less than about 4 percent crystallinity and typically between about 4 and 7 mm in thickness
- a preform usually has an outside surface area that is at least an order of magnitude smaller than the outside surface of the final container.
- the preform is reheated to an orientation temperature that is typically 30°C above the glass transition temperature (T g ).
- the reheated preform is then placed into a bottle blow mold and, by stretching and inflating with high-pressure air, formed into a heated bottle.
- the blow mold is maintained at a temperature between about 115°C and 200°C, usually between about 120°C and 160°C.
- the compressed air is turbulently released from the bottle by the balayage technique to facilitate cooling of the heated bottle. It is believed that the preforms according to the present invention can be blow molded into low-shrinkage bottles using lower-than-conventional pressure for the compressed air.
- the preforms are blow molded into low-shrinkage bottles within a cycle time of less than about 6 seconds (i.e., at normal production rates).
- branching agents may be included in small amounts (e.g., less than about 2,000 ppm) to increase polymerization rates and improve bottle-making processes.
- Chain branching agents can be introduced, for example, during esterification or melt phase polymerization.
- less than 0.1 mole percent branching agent is included in the polyethylene terephthalate resins of the present invention.
- the term "branching agent” refers to a multifunctional monomer that promotes the formation of side branches of linked monomer molecules along the main polymer chain. See Odian, Principles of Polymerization, pp. 18-20 (Second Edition 1981).
- the chain branching agent is preferably selected from the group consisting of trifunctional, tetrafunctional, pentafunctional and hexafunctional alcohols or acids that will copolymerize with polyethylene terephthalate.
- a trifunctional branching agent has one reactive site available for branching
- a tetrafunctional branching agent has two reactive sites available for branching
- a pentafunctional branching agent has three reactive sites available for branching
- a hexafunctional branching agent has four reactive sites available for branching.
- Acceptable chain branching agents include, but are not limited to, trimesic acid (C 6 H 3 (COOH) 3 ), pyromellitic acid (C 6 H 2 (COOH) 4 ), pyromellitic dianhydride, trimellitic acid, trimellitic anhydride, trimethylol propane (C 2 HsC(CH 2 OH) 3 ), ditrimethylol propane (C 2 H 5 C(CH 2 OH) 2 C 2 H 4 OC(CH 2 OH) 2 C 2 H 5 ), dipentaerythritol
- Preferred aromatic chain branching agents — aromatic rings appear to curb stress nucleation — include trimellitic acid (TMLA), trimellitic anhydride (TMA), pyromellitic acid (PMLA), pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic acid, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic acid, and naphthalene tetracarboxylic dianhydride, as well as their derivatives:
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0418725-3A BRPI0418725A (en) | 2004-04-06 | 2004-11-24 | methods of preparing titanium catalyzed polyethylene terephthalate resins |
CA002562046A CA2562046A1 (en) | 2004-04-06 | 2004-11-24 | Methods of making titanium-catalyzed polyethylene terephthalate resins |
MXPA06011692A MXPA06011692A (en) | 2004-04-06 | 2004-11-24 | Methods of making titanium-catalyzed polyethylene terephthalate resins. |
US11/466,066 US20070059465A1 (en) | 2004-05-20 | 2006-08-21 | Polyester Resins for High-Strength Articles |
US12/334,851 US20090176046A1 (en) | 2004-05-20 | 2008-12-15 | Polyester Resins for High-Strength Articles |
US12/622,502 US20100221472A1 (en) | 2004-05-20 | 2009-11-20 | Polyester Resins for High-Strength Articles |
US12/978,783 US8304510B2 (en) | 2003-05-21 | 2010-12-27 | Polyester resins for high-strength articles |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US55998304P | 2004-04-06 | 2004-04-06 | |
US60/559,983 | 2004-04-06 | ||
US57302404P | 2004-05-20 | 2004-05-20 | |
US10/850,269 US20050261462A1 (en) | 2004-05-20 | 2004-05-20 | Methods of making titanium-catalyzed polyester resins |
US60/573,024 | 2004-05-20 | ||
US10/850,269 | 2004-05-20 | ||
US10/850,918 US7129317B2 (en) | 2003-05-21 | 2004-05-21 | Slow-crystallizing polyester resins |
US10/850,918 | 2004-05-21 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/850,269 Continuation-In-Part US20050261462A1 (en) | 2003-05-21 | 2004-05-20 | Methods of making titanium-catalyzed polyester resins |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/466,066 Continuation-In-Part US20070059465A1 (en) | 2003-05-21 | 2006-08-21 | Polyester Resins for High-Strength Articles |
Publications (3)
Publication Number | Publication Date |
---|---|
WO2005103110A2 true WO2005103110A2 (en) | 2005-11-03 |
WO2005103110A3 WO2005103110A3 (en) | 2006-02-23 |
WO2005103110B1 WO2005103110B1 (en) | 2006-04-13 |
Family
ID=35197542
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/039726 WO2005103110A2 (en) | 2003-05-21 | 2004-11-24 | Methods of making titanium-catalyzed polyethylene terephthalate resins |
Country Status (4)
Country | Link |
---|---|
BR (1) | BRPI0418725A (en) |
CA (1) | CA2562046A1 (en) |
MX (1) | MXPA06011692A (en) |
WO (1) | WO2005103110A2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008078078A1 (en) * | 2006-12-22 | 2008-07-03 | Colormatrix Holdings, Inc. | Polymer compositions and aricles having improved reheat characteristics |
US7763701B2 (en) | 2006-07-11 | 2010-07-27 | Wellman, Inc. | Composite solid phase polymerization catalyst |
US8338505B2 (en) | 2005-11-15 | 2012-12-25 | Dak Americas Mississippi Inc. | Alumina-enhanced polyester resins and methods for making the same |
US8791225B2 (en) | 2008-06-06 | 2014-07-29 | Dak Americas Mississippi Inc. | Titanium-nitride catalyzed polyester |
EP2118166B1 (en) | 2007-02-02 | 2018-04-25 | Grupo Petrotemex, S.A. De C.V. | Polyester polymers with low acetaldehyde generation rates and high vinyl ends concentration |
CN114195990A (en) * | 2021-11-25 | 2022-03-18 | 天津万华股份有限公司 | Low-precipitation matte polyester chip for laminating flexible circuit board and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050153086A1 (en) * | 2003-05-21 | 2005-07-14 | Moore Tony C. | Polyester preforms useful for enhanced heat-set bottles |
-
2004
- 2004-11-24 WO PCT/US2004/039726 patent/WO2005103110A2/en active Application Filing
- 2004-11-24 CA CA002562046A patent/CA2562046A1/en not_active Abandoned
- 2004-11-24 BR BRPI0418725-3A patent/BRPI0418725A/en not_active Application Discontinuation
- 2004-11-24 MX MXPA06011692A patent/MXPA06011692A/en active IP Right Grant
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050153086A1 (en) * | 2003-05-21 | 2005-07-14 | Moore Tony C. | Polyester preforms useful for enhanced heat-set bottles |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8338505B2 (en) | 2005-11-15 | 2012-12-25 | Dak Americas Mississippi Inc. | Alumina-enhanced polyester resins and methods for making the same |
US7763701B2 (en) | 2006-07-11 | 2010-07-27 | Wellman, Inc. | Composite solid phase polymerization catalyst |
US7829656B2 (en) | 2006-07-11 | 2010-11-09 | Wellman, Inc. | Solid phase polymerization catalyst system |
WO2008078078A1 (en) * | 2006-12-22 | 2008-07-03 | Colormatrix Holdings, Inc. | Polymer compositions and aricles having improved reheat characteristics |
US8445086B2 (en) | 2006-12-22 | 2013-05-21 | Colormatrix Holdings, Inc. | Polymer compositions and articles having improved reheat characteristics |
EP2118166B1 (en) | 2007-02-02 | 2018-04-25 | Grupo Petrotemex, S.A. De C.V. | Polyester polymers with low acetaldehyde generation rates and high vinyl ends concentration |
US8791225B2 (en) | 2008-06-06 | 2014-07-29 | Dak Americas Mississippi Inc. | Titanium-nitride catalyzed polyester |
CN114195990A (en) * | 2021-11-25 | 2022-03-18 | 天津万华股份有限公司 | Low-precipitation matte polyester chip for laminating flexible circuit board and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
WO2005103110A3 (en) | 2006-02-23 |
CA2562046A1 (en) | 2005-11-03 |
BRPI0418725A (en) | 2007-09-11 |
MXPA06011692A (en) | 2006-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1639034B1 (en) | Slow-crystallizing polyester resins | |
US7094863B2 (en) | Polyester preforms useful for enhanced heat-set bottles | |
US8304510B2 (en) | Polyester resins for high-strength articles | |
JP2007504352A5 (en) | ||
US8791225B2 (en) | Titanium-nitride catalyzed polyester | |
US7829656B2 (en) | Solid phase polymerization catalyst system | |
US7238770B2 (en) | Methods of making imide-modified polyester resins | |
US20080009574A1 (en) | Polyamide-Polyester Polymer Blends and Methods of Making the Same | |
US20070225410A1 (en) | Imide-Modified Polyester Resins | |
US8524343B2 (en) | Polyester resins for high-efficiency injection molding | |
US20050261462A1 (en) | Methods of making titanium-catalyzed polyester resins | |
WO2006079044A2 (en) | Improved polyamide-polyester polymer blends and methods of making the same | |
WO2005103110A2 (en) | Methods of making titanium-catalyzed polyethylene terephthalate resins | |
JP2004026853A (en) | Polyester composition lowering uv-ray transmittance and pet-bottle produced therefrom | |
CN1954012A (en) | Methods of making titanium-catalyzed polyethylene terephthalate resins | |
JP2006160336A (en) | Polyester-resin-made bottle | |
MXPA06008645A (en) | Imide-modified polyester resins and methods of making the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
B | Later publication of amended claims |
Effective date: 20060207 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11466066 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2562046 Country of ref document: CA Ref document number: 2843/KOLNP/2006 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2006/011692 Country of ref document: MX |
|
NENP | Non-entry into the national phase in: |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200480043027.3 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 11466066 Country of ref document: US |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 69(1) EPC |
|
122 | Ep: pct application non-entry in european phase | ||
ENP | Entry into the national phase in: |
Ref document number: PI0418725 Country of ref document: BR |