WO2001014452A1 - Preparation de polyesters utilisant des catalyseurs a base d'antimoine et composes phosphores acides - Google Patents

Preparation de polyesters utilisant des catalyseurs a base d'antimoine et composes phosphores acides Download PDF

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Publication number
WO2001014452A1
WO2001014452A1 PCT/US1999/019385 US9919385W WO0114452A1 WO 2001014452 A1 WO2001014452 A1 WO 2001014452A1 US 9919385 W US9919385 W US 9919385W WO 0114452 A1 WO0114452 A1 WO 0114452A1
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Prior art keywords
antimony
process according
acid
additive
ppm
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PCT/US1999/019385
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English (en)
Inventor
Mary Therese Jernigan
Carol Julliard Greene
Perry Murdaugh
Alan Wayne White
Cheuk Yau
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Eastman Chemical Company
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Priority to PCT/US1999/019385 priority Critical patent/WO2001014452A1/fr
Publication of WO2001014452A1 publication Critical patent/WO2001014452A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • 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
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof

Definitions

  • the present invention relates to processes for producing polyester resins and in particular poly(ethylene) terephthalate (PET) containing low levels of phosphorus containing additives that is suitable for use in a variety of applications including the manufacture of articles such as containers.
  • PET poly(ethylene) terephthalate
  • PET poly(ethylene terephthalate)
  • PET or modified PET is a polymer of choice for making beverage and food containers, particularly carbonated beverage containers.
  • Poly(ethylene terephthalate) may be derived from multistep processes well known in the art which may include the direct esterification of ethylene glycol and terephthalic acid.
  • PET can be modified with additional acidic and/or glycol comonomers, e.g., isophthalic acid (or dimethyl isophthalate), 1,4-cyclohexanedimethanol (CHDM), and the like. Modifying PET with additional comonomers may improve some of the physical properties of the resulting polyesters and provide particularly desired properties in an article formed from the polyester particularly in the areas of crystallization and processability.
  • Polyesters such as PET are typically formed via three-stage processes.
  • the three preferred stages are often referred to as the esterification stage, the prepolymer stage, and the polycondensation stage.
  • Each of the stages can employ catalysts and certain additives.
  • catalysts include titanium, gallium, germanium, tin, and antimony compounds.
  • additives is also known in the art. Additives that are recognized in the art include phosphorus-containing stabilizers such as phosphates and phosphoric acid. In this regard, such phosphorus-containing additives are considered interchangeable.
  • Rubber Company discloses process for producing high clarity colorless polyesters which include the use of polycondensation catalysts, cobalt-containing compounds and phosphorus-containing additives.
  • German Patent Application 195 37 930 Al opened to public inspection on
  • U.S. Patent 5,243,022 issued Sept. 7, 1993 and assigned to Korea Institute of Science and Technology, discloses a method for forming polyesters that involves forming prepolymers from a first portion of esterification product in the presence of certain catalysts and stabilizers. The prepolymers are then polycondensed together with a second portion of esterification product to form the polyester.
  • U.S. Patent 5, 235,027 issued Aug. 10, 1993 and assigned to Zirnmer Aktiegesellschaft, discloses a process for making a modified copolyethylene terephthalate that includes the addition of a phosphorus-oxygen compound before polycondensation in an amount that corresponds to a Sb: P weight ratio of at least four.
  • the present invention is based, in part, on the surprising discovery that the choice of phosphorus-containing additive, when employed in connection with certain polymerization catalysts, can have a significant impact on reaction rate of the polymerization process as well as the clarity of the resulting polyester. Further, it was surprisingly found that the optimal relative addition sequence of the catalyst and phosphorus-containing additive was impacted by the both choice and level of phosphorus-containing additive.
  • One aspect of the present invention involves a process for making a polyester resin including the steps of:
  • step (b) polymerizing the product of step (a) under conditions effective to provide a polyester resin, wherein the polymerization step (b) occurs in the presence of (i) an antimony-based polymerization catalyst and (ii) an acidic phosphorus-containing additive, with the additive (ii) being added prior to the catalyst (i) so as to provide a polyester resin that is at least substantially free of inorganic compounds formed from a reaction of the catalyst (i) and additive (ii).
  • the amount of additive is preferably not greater than about 45 ppm based on elemental phosphorus in the resulting polyester.
  • the process can include a prepolymer stage between steps (a) and
  • the process can further include additional step such as solid-phase polymerization of the polyester resin from step (b).
  • the polymerization step (b) is preferably performed in the absence of added cobalt compound(s).
  • Another aspect of the present invention relates to a process that includes (a) esterifying at least one dicarboxylic acid component and at least one diol component; and polymerizing the product of step (a) under conditions effective to provide a polyester resin, wherein the polymerization step (b) occurs in the presence of (i) an antimony- based polymerization catalyst and (ii) an acidic phosphorus-containing additive, with the catalyst (i) being added after, the additive (ii), and the acidic phosphorus containing additive (ii) is added sufficiently before the polycondensation catalyst (i) such that the additive (ii) can react with the at least one diol.
  • Yet another aspect of the present invention include process for making polyester resin that includes (a) esterifying at least one dicarboxylic acid component and at least one diol component; and (b) polymerizing the product of step (a) under conditions effective to provide a polyester resin, wherein the polymerization step (b) occurs in the presence of (i) an antimony-based polymerization catalyst and (ii) an acidic phosphorus-containing additive, with the catalyst (i) being added after, the additive (ii), because of the order of additive employed in the present invention, the reaction rate of the polymerization step (b) is relatively insensitive to the level of additive (ii).
  • the present invention relates to a polyester, and in particular, a poly(ethylene terephthalate) (PET) resin or a modified PET resin which is preferably made by the inventive process.
  • PET poly(ethylene terephthalate)
  • the polyester contains elemental phosphorus in an amount not greater than 45 ppm and organic toners in an amount of about 0.5 to about 10 ppm.
  • polymer resulting from step (b) is preferably at least substantially free of antimony phosphate compounds.
  • the polyester resin preferably has an intrinsic viscosity of about 0.4 to 1.2 dL/g measured at 25 C by dissolving 250 mg of polyester in 50 mL of a solvent consisting of a 60:40 ratio by weight of phenol and 1,1,2,2-tetrachloroethane.
  • Fig. 1 illustrates the effect on phosphorus level on DEG level of the esterification product when phosphoric acid is added before esterification stage
  • Fig. 2 illustrates the effect on reaction rate, as represented by time in the polycondensation stage, of changing phosphorus and antimony levels when acidic phosphorus-containing compounds are introduced prior to the antimony catalyst;
  • Fig. 3 illustrates the effect on reaction rate, as represented by time in the polycondensation stage, of changing phosphorus and antimony levels when acidic phosphorus-containing compounds are introduced after the antimony catalyst.
  • the present invention relates to a process for making polyester resins and in particular, poly(ethylene terephthalate), which employs the use of acidic phosphorus- containing additives.
  • the amount, and point of introduction, for the acidic phosphorus-containing additives can be optimized so as to provide for an improved process, e.g., a decreased reaction time, and a desired product, e.g., a polyester having improved clarity.
  • acidic phosphorus-containing additives such as phosphoric acid
  • non-acidic phosphorus-containing compounds such as phosphate triesters.
  • they can have very different, effects on the polymerization stage.
  • acidic phosphorus-containing compounds are introduced prior to certain polymerization catalysts, one can provide for relatively high reaction rates at certain phosphorus levels.
  • the process of the present invention can provide for the reduction, and possibly even elimination, of antimony phosphate crystals in the resulting polyester. This ability to reduce the amount, size or both of antimony phosphate crystals can effectively reduce the particulate haze in the polyester.
  • polyesters may be prepared in accordance with techniques that are recognized in the art.
  • polyesters are any crystallizable polyester homopolymer or copolymer, preferably those polyesters suitable for use in packaging, and particularly food packaging.
  • polyesters are generally known in the art and may be formed from aromatic dicarboxylic acids, esters of dicarboxylic acids, anhydrides of dicarboxylic esters, glycols, and mixtures thereof. More preferably the polyesters are formed from diacids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and mixtures thereof, and diols such as ethylene glycol, diethylene glycol, 1,4- cyclohexane dimethanol, 1 ,4-butanediol, and mixtures thereof.
  • diacids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and mixtures thereof
  • diols such as ethylene glycol, diethylene glycol, 1,4- cyclohexane dimethanol, 1 ,4-butanediol, and mixtures thereof.
  • the process of the present invention can produce the produce the polyesters and "modified” polyesters.
  • modified it is meant that the preferred diacids and/or diols are substituted with one or more diacid or diol components.
  • the preferred diol e.g., ethylene glycol in the case of PET
  • the preferred acid component e.g., terephthalic acid, in the case of PET
  • the dicarboxylic acid component of the polyester may optionally be substituted with up to about 20 mole percent of one or more different dicarboxylic acids.
  • additional dicarboxylic acids include aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, or cycloahphatic dicarboxylic acids preferably having 8 to 12 carbon atoms.
  • dicarboxylic acids to be included with terephthalic acid are: phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 1,4- cyclohexanedicarboxylic acid, 1,3-cyclohexanedi-carboxylic acid, stilbene dicarboxylic acid, cyclohexanediacetic acid, 1,12-dodecanedioic acid, diphenyl-4, 4'- dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, mixtures thereof and the like.
  • the glycol component may optionally be substituted with up to about 20 mole percent, of one or more different diols other than ethylene glycol.
  • additional diols include cycloahphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms.
  • diols examples include: diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane- 1,2-diol, propane- 1,3-diol, butane- 1,4-diol, pentane-l,5-diol, hexane-l,6-diol, 3- methylpentanediol-(2,4), 2-methylpentanediol-(l ,4), 2,2,4-trimethylpentane-diol-(l ,3), 2-ethylhexanediol-(l,3), 2,2-diethylpropane-diol-(l,3), hexanediol-(l,3), 1,4-di- (hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy- 1,1,3,3-tetramethyl-
  • the process of the present invention can employ art-recognized steps or stages in forming polyesters.
  • the preferred stages are:
  • esterification stage including but not necessarily limited to direct esterification
  • a prepolymer stage also including but not limited to polycondensation, is preferably performed between the esterification and polymerization stages.
  • each of stages may include one or more steps or substages.
  • the esterification and/or prepolymer stages may each include one or more reaction steps or substages having differing reaction conditions, e.g., progressively lower pressures and temperature.
  • the esterification stage typically involves heating a mixture of one or more dicarboxylic acids, preferably aromatic dicarboxylic acids, and one or more diols under suitable conditions and in the optional presence of esterification catalysts.
  • suitable conditions include temperatures in the range of about 200°C to about 300°C, preferably 240°C to about 280°C, and pressures of about 0 to about 100, preferably about 0 to about 50 psig
  • the optional esterification catalysts can be used alone or in combination. When used the total amount of catalyst is less than about 200 ppm, more preferably less than 100 ppm, on an elemental basis in the resulting polymer. It is more preferred that no catalyst be employed. Suitable colorants may also be added at this point to control the final color of the polyester.
  • the reaction is typically conducted for about 1 to about 4 hours. It should be understood that generally the lower the reaction temperature, the longer the reaction will have to be conducted.
  • the esterification stage typically produces a monomer and oligomer mixture continuously in a series of one or more reactors. Alternately, the monomer and oligomer mixture could be produced in one or more batch reactors.
  • a prepolymer stage the mixture of polyester monomer and oligomers undergoes a suitable polymerization step, typically melt-phase polycondensation, to produce a low molecular weight precursor polymer.
  • the precursor polymer is produced in a series of one or more reactors operating at elevated temperatures. This can involve the a single stage, or one or more substages.
  • the prepolymer stage can involve the use of one or more reactors operated continuously, one or more batch reactors or even one or more reaction steps or substages performed in a single reactor vessel.
  • the precise reaction conditions are dependent upon the nature of the reactants and the final product. However, to facilitate removal of excess glycols, water, alcohols, aldehydes, and other reaction products, the reactors are typically run under a vacuum or purged with an inert gas. Inert gas is any gas which does not cause unwanted reaction or product characteristics at reaction conditions. Suitable gases include, but are not limited to CO2, argon, helium and nitrogen.
  • the prepolymer stage is typically conducted at a temperature less than about 300°C, and preferably between about 240°C and about 290°C at a pressure sufficient to aid in removing reaction products such as ethylene glycol.
  • the next stage which is the polymerization stage, also typically involves the melt-phase polycondensation of the prepolymer product.
  • the polymerization stage typically involves the same basic chemistry as the prepolymer stage, the fact that the size of the molecules, and thus the viscosity differs, means that the reaction conditions also differ.
  • reaction conditions A wide variety of reaction conditions, are employed in the art, and as such they all will not be described here.
  • the present invention contemplates the use of the wide range of polymerization options that are recognized in the art as being suitable for use with polyesters.
  • the primary requirement for the polymerization stage according to the present invention is that it be performed in the presence of both a suitable catalyst and a phosphorus additive.
  • the additive is introduced prior to the catalyst. While the exact point of introduction for the additive is not critical as long as the additive can suitably react with the diol(s) prior to introduction of the catalyst. According to the present invention, catalyst is added any point after the additive In some embodiments, it is preferred that the additive be introduced, during, the esterification stage, or prior to or during a prepolymer stage.
  • the catalyst be introduced at any point after the additive and preferably, immediately prior to, or during, the prepolymer stage as long as it is introduced before the polymerization stage and sufficiently after the additive to allow the additive to react with the diol(s).
  • the catalyst it is more preferred to have the phosphorus introduced in a substage prior to the substage when the catalyst is added.
  • the amount of DEG can be controlled. That is, the later the additive is introduced the less DEG would be expected to be produced. Steps could be taken to reduce the level of DEG formed.
  • the addition point of the acidic phosphorus-containing additive may be optimized to reduce DEG formation.
  • the rate of diethylene glycol formation is mainly proportional to the concentration of ethylene glycol (EG) end groups. As esterification progresses, the DEG will increase, and there will be fewer EG end groups. Adding the acidic phosphorus-containing compound later in the process may minimize DEG formation.
  • there are a variety of art-recognized techniques for reducing the DEG concentration including that discussed in U.S. Patent No. 5,252,513, which is incorporated by reference in its entirety.
  • the additive be introduced late in the stage, preferably after 90%, more preferably after 95% and still more preferably after 98% conversion in the selected stage.
  • phosphoric acid may be added between the first and second esterification stage while the antimony is added after the second esterification stage and before the first prepolymer stage. Further, phosphoric acid may be added after the last esterification stage and before the first prepolymer stage while the antimony is added during the prepolymer stage.
  • reaction step or sub-stage is employed in the prepolymer stage, it is more preferred to have the catalyst introduced prior to the final reaction step a sub-stage in order to provide optimal mixing time prior to the polymerization step.
  • the preferred polymerization catalyst for use in the process of the present invention is an antimony-based polymerization catalyst.
  • Suitable antimony based catalyst include antimony (III) and antimony (N) compounds recognized in the art and in particular, diol-soluble antimony (III) and antimony (V) compounds.
  • Other suitable compounds include those antimony compounds that react with, but are not necessarily soluble in, the diols, with examples of such compounds including antimony (III) oxide.
  • antimony catalysts include antimony (III) oxide and antimony (III) acetate, antimony (III) glycolates, antimony (III) ethyleneglycoxide and mixtures thereof, with antimony (III) oxide being preferred.
  • the preferred amount of catalyst added is that effective to provide an elemental antimony level of between about 75 and about 400 ppm by weight of the resulting polyester.
  • the phosphorus-containing additive employed in the present invention can be any acidic phosphorus-containing compound recognized in the art. Suitable examples of such additives include phosphoric acid, phosphorous acid, polyphosphoric acid, acidic phosphite esters, acidic phosphate esters such as phosphate mono- and di- esters, and mixtures thereof, among others.
  • the acidic phosphorus-containing additive is present in an amount effective to provide a desired reaction rate.
  • the polymerization rate can be largely insensitive to phosphorus level and can even be optimized for certain phosphorus levels. For example, it was found for antimony catalyst corresponding to elemental antimony levels on the order of 210 ppm, and the phosphorus levels were about 20-25 ppm, reaction rates were comparable or better than reaction rates after the reverse addition order.
  • the acidic phosphorus-containing additive can also be present in an amount effective to provide a polyester resin that is at least substantially free of inorganic compounds that are reaction products of the catalyst and the additive and can cause haze in the polyester. That is, under certain conditions, a polycondensation catalyst(s) and an acidic phosphorus-containing additive(s) can react with each other to produce certain inorganic compounds, such as antimony phosphate. Such inorganic compounds can cause particulate haze in polyesters.
  • the formation of such inorganic compounds can also be reduced or even eliminated.
  • a polycondensation process minimizes the formation of such inorganic compounds, the process is more likely to produce polyesters without undesirable levels of particulate haze, which precludes clarity. Accordingly, the process of the present invention is capable of producing a polyester resin "at least substantially free" of such inorganic compounds, and in particular, at least substantially free of antimony phosphates.
  • the polyester resin does not include levels of the above-discussed inorganic compounds such as antimony phosphates; that create a particulate haze which can have a negative visual impact upon the resin melt or articles formed from the resin.
  • the preferred amount of acidic phosphorus-containing additive is that effective to provide a relatively low elemental phosphorus level, i.e., not greater than about 75 ppm based on the weight of the polyester. Suitable levels fall both in the "high” end of that range, e.g., about 45 to about 75 ppm, “mid” levels of 20-45 ppm, and “low” end, of the range, e.g., less than about 15 ppm. Although the chemistry does not impose a lower limit, the amount is typically not less than 1 ppm. The foregoing amounts are by weight of elemental phosphorus in the resulting polyester.
  • the phosphorus-containing additive is preferably introduced in a solution of the diol(s).
  • any concentration that is capably providing the desired phosphorus level can be employed. Suitable concentrations include those greater than about 1 % wt., preferably about 3 to about 15 % by weight of the additive in the diol.
  • Temperatures for the polymerization stage are generally between about 240°C to about 300°C and a pressure between about 0 and about 2 mm Hg.
  • the polymer is pelletized.
  • Precursor IN. is generally below about 0.7 to maintain good color.
  • the target I.N. is generally selected to balance good color and minimize the amount of solid stating which is required.
  • the I.N. of a polyester of this invention is from about 0.40 dl/g to about 1.2 dl/g.
  • Inherent viscosity was measured at 25°C using 0.50 grams of polymer per 100 ml of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane .
  • the resulting polymer can then be subjected to further polymerization reaction, e.g., solid phase polymerization (also know as "solid-stating") by techniques which are known in the art and as such are not described in detail here.
  • further polymerization reaction e.g., solid phase polymerization (also know as "solid-stating") by techniques which are known in the art and as such are not described in detail here.
  • additives normally used in polyesters may be used if desired.
  • additives include, but are not limited to colorants, pigments, carbon black, glass fibers, fillers, impact modifiers, antioxidants, stabilizers, flame retardants, reheat aids, acetaldehyde reducing compounds and the like.
  • organic toners e.g., blue and red organic toners, such as those described in U.S. Patents 5,372,864 and 5,384,377, which are incorporated by reference, can be used. As discussed in these U.S.
  • suitable blue toners include substituted l,4-bis(2,6-dialkylanilino) anthraquinones) while suitable red toners include anthraquinone and anthrapyridone (3-H- dibenz[f,ij]isoquinoline-2,7-dione) compounds.
  • the total amount of organic toners in the polymer is preferably 0.5 to about 10 ppm. To this end, about 0.5 to about 3 ppm of organic red toner(s) and about 1 to about 7 ppm of organic blue toner(s) are more preferred.
  • the polyester is preferably devoid of any added cobalt compounds. That is, while certain very minor amounts of certain cobalt compounds may be present in the diacid(s) and/or diol(s) starting materials, no cobalt-containing compounds are added during the process. Moreover, the polyester is preferably devoid of zinc, gallium, and silicon compounds.
  • the resin may also contain small amounts of polyfunctional (comonomers, e.g., trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
  • polyfunctional comonomers e.g., trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
  • polyfunctional comonomers e.g., trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids
  • polyesters according to the present invention can be used in forming a variety of articles including sheets, films, tubing, profiles, preforms, fibers, woven and shaped articles, such as containers, and thermoformed articles such as trays and the like.
  • TPA Terephthalic acid
  • EG plant grade ethylene glycol
  • CHDM distilled cyclohexanedimethanol
  • the esterification was done in a continuous unit and was followed by batch-wise polycondensation.
  • the esterification was carried out in two continuous reactors connected in series (Rl and R2).
  • a third vessel (R3) was used as a flash tank and for collection of the esterification product.
  • the fixed volume reactors had approximately a 2:1 volume ratio with 2230 mL in Rl and 1100 mL in R2.
  • the feed mole ratio of total glycols to terephthalic acid was 1.35.
  • the amount of CHDM in the feed was 1.5 mole percent of the terephthalic acid in the feed slurry, with the excess diol in the feed slurry being ethylene glycol.
  • Slurry ingredients were mixed in a blender and added to a feed tank. The feed rate was 10 mL/min.
  • the temperature target in Rl was 262 deg. C.
  • the temperature target in R2 was 267 deg. C.
  • the pressure targets for Rl and R2 were 36.5 PSIG and 18.5 PSIG, respectively. Substantially all the ethylene glycol vaporized from Rl was condensed and returned directly to Rl .
  • the additive or catalyst solutions were made per the following procedures.
  • a phosphorus concentration target of 3.5 wt. % was used for the phosphorus solution.
  • Phosphoric acid 13.03 g of 85 %, Food Grade, FMC
  • Ethylene glycol was added until the total solution weight was 100.00 g.
  • a magnetic stir bar was added, and the mixture was stirred.
  • a solution of antimony oxide in ethylene glycol was made with a target antimony concentration of 1.2 wt. %.
  • Antimony oxide (7.37 g, Fisher) was added into a tared, three-necked, 1-L round-bottomed flask. Ethylene glycol was added until the total solution weight was 500.00 g.
  • the flask was fitted with a heating mantle, condenser, a stopper and a paddle stirrer. The condenser was connected to a nitrogen source and vented through a bubbler to keep air from entering the system. An insulating jacket was placed on the exposed upper portion of the flask. The flask was heated with stirring until the EG was refluxing vigorously. The mixture was held at reflux for at least 3 hours. The mixture was cooled and filtered through a 0.22 micron cellulose acetate, supported plain filter by Micron Separations, Inc.
  • Oligomers made with a given additive or catalyst were produced in the continuous unit in a block to minimize the magnitude of the transition required.
  • the target levels were randomized. In the interest of minimizing transitions, the highest target level was not run at the beginning of a block. The unit was run for twenty-four hours to make each oligomer. Product was collected in a nitrogen-purged, covered, steel beaker, surrounded by dry ice. The beaker was changed about every three hours. The materials from the last three beakers - representing the last 9 hours of a run - were ground and analyzed. Before polymerization, the beakers judged to be comparable were combined in a large bag with shaking.
  • the carboxyl end groups were determined by titration with base. Additive and catalyst levels were measured by X-ray fluorescence (XRF). Degree of polymerization and mole % reacted CHDM were obtained by NMR spectroscopy of a phenol and 1,1,2,2-tetrachloroethane solution. Percent conversion calculations combined carboxyl end groups and NMR data. After samples were hydrolyzed and silylated, the weight percent of diethylene glycol was measured via a gas chromatography method. Molecular weights were determined by gel permeation chromatography.
  • Example 1 Esterification in the Presence of a Target of 150 ppm Antimony
  • the slurry put in the feed tank consisted of 3270 g of Amoco TPA, 1585 g of
  • Example 2 Esterification in the Presence of a Target of 250 ppm Antimony
  • the slurry put in the feed tank consisted of 3270 g of Amoco TPA, 1556 g of
  • Example 3 Esterification in the Presence of a Target of 10 ppm Phosphorus
  • the slurry put in the feed tank consisted of 3270 g of Amoco TPA, 1630 g of
  • Example 4 Esterification in the Presence of a Target of 62 ppm Phosphorus
  • the slurry put in the feed tank consisted of 3270 g of Amoco TPA, 1625 g of
  • the melt-phase polymerization stage of the designed experiment was run in random order. Esterification products were prepared per the preceding section. Ground esterification product (206 g) was weighed into a one-liter, single-necked, round-bottomed flask. A 316L stainless steel paddle stirrer and a glass polymer head were attached to the flask. After attaching the polymer head to a side arm and a purge hose, two nitrogen purges were completed.
  • the polymerization reactor was operated under the control of a CAMILETM automation system. After a molten bath of Belmont metal was raised to surround the flask, the CAMILETM array was initiated. See the following table for the polymerization conditions. In a CAMILETM array, a ramp is defined as a linear change of vacuum, temperature or stir speed during the specified stage time. After the melting stage (# 2) ended, a 5-minute catalyst addition stage (# 3) began, and the appropriate additive or catalyst solution was added within the last minute of this stage. The additive and catalyst solutions were prepared as described in the Esterification Procedure section. The stirring system was automatically calibrated after stage four and prior to stage five. The finisher stage (#13) was terminated when the power reached 4.15% three times. Polymers were cooled to ambient temperature.
  • the polymers were chopped and ground to pass a 3 mm screen. Ground polymers were shaken on a 40-mesh sieve fitted with a lid and pan. The lid and the pan were removed. A second 40-mesh sieve was placed on top of the first. Compressed air was blown through the pair of sieves. This dust removal process reduced the number of fines that adhered to larger particles during the sieving process. The fines would solid-phase polymerize quickly and adversely affect comparisons.
  • the +40 mesh portion of each polymer was shaken through a series of sieves: 10, 12, 14, 16, 18 and 20 mesh. The polymer fraction on each sieve was weighed.
  • This standard blend had a total weight of 80.5 g where 8.4 grams were -10/+12 mesh, 32.54 grams were -12/+14 mesh, 20.27 grams were - 14/+16 mesh, 14.48 grams were -16/+18 mesh, and 4.81 grams were -18/+20 mesh grinds. Color was measured on the precursor blend.
  • the inherent viscosity (IN) was measured at 25 deg. C by dissolving 0.50 grams of polymer in 100 mL of 60% phenol and 40% 1,1,2,2-tetrachloroethane by weight. Additive and catalyst levels were measured by X-ray fluorescence (XRF). The carboxyl end groups were determined by titration with base. Color was measured using a HunterLab Color test, which was reported in CIELAB units. The diethylene glycol (DEG) level was measured by dissolving 22 to 28 mg of polymer in a solvent mixture consisting of 70% chloroform-d and 30% trifluoroacetic acid-d and obtaining the ⁇ MR spectrum on a 500 MHz instrument.
  • XRF X-ray fluorescence
  • Ground esterification product (Sample 18, 206 g) was weighed into a one-liter, single-necked, round-bottom flask. Phosphoric acid (0.03 mL of 3.60 wt./wt. % P solution) was added within the last minute of stage 3. The finisher time (length of stage 13) was 93 minutes.
  • Ground esterification produet (Sample 18, 206 g) was weighed into a one-liter, single-necked round-bottom flask. Phosphoric acid (0.27 mL of 3.60 wt./wt. % P solution) was added within the last minute of stage 3. The finisher time (length of stage 13) was 224 minutes (3-7 hrs).
  • Ground esterification product (Sample 9, 206 g) was weighed into a one-liter, single- necked round-bottom flask. Phosphoric acid (0.03 mL of 3.60 wt./wt. % P solution) was added within the last minute of stage 3. The finisher time (length of stage 13) was 60 minutes.
  • Example 8 Polymerization of Esterification Product #9 (232 ppm Sb) with Prepolymer Addition of 49 ppm of Phosphorus
  • Ground esterification product (Sample 9, 206 g) was weighed into a one-liter, single- necked round-bottom flask. Phosphoric acid (0.27 mL of 3.60 wt./wt. % P solution) was added within the last minute of stage 3. The finisher time (length of stage 13) was 124 minutes.
  • Ground esterification product (Sample 20, 206 g) was weighed into a one-liter, single- necked round-bottom flask.
  • Antimony glycolate (2.3 mL of 1.11 wt./wt. % Sb solution) was added within the last minute of stage 3.
  • the finisher time (length of stage 13) was 104 minutes.
  • Example 10 Polymerization of Esterification Product #6 (48 ppm P) with Prepolymer Addition of 135 ppm of Antimony
  • Ground esterification product (Sample 6, 206 g) was weighed into a one-liter, single- necked round-bottom flask.
  • Antimony glycolate (2.3 mL of 1.11 wt./wt. % Sb solution) was added within the last minute of stage 3.
  • the finisher time (length of stage 13) was 119 minutes.
  • Example 11 Polymerization of Esterification Product #20 (7 ppm P) with Prepolymer Addition of 232 ppm of Antimony
  • Ground esterification product (Sample 20, 206 g) was weighed into a one-liter, single- necked round-bottom flask.
  • Antimony glycolate (4.3 mL of 1.11 wt./wt. %Sb solution) was added within the last minute of stage 3.
  • the finisher time (length of stage 13) was 76 minutes.
  • Ground esterification product (Sample 6, 206 g) was weighed into a one-liter, single- necked round-bottom flask.
  • Antimony glycolate (4.0 mL of 1.19 wt./wt. % Sb solution) was added within the last minute of stage 3.
  • the finisher time (length of stage 13) was 88 minutes.
  • Figures 2 & 3 were generated. The numbers on these figures correspond to finisher time in minutes.
  • Figure 2 illustrates the effect on finisher time of changing phosphorus levels and antimony levels when phosphoric acid is added just prior to the prepolymer stage.
  • Figure 3 illustrates the effect on finisher time of changing phosphorus levels and antimony levels when phosphoric acid is added up front to the TPA/EG/CHDM paste prior to the esterification stage.
  • the maximum level of phosphoric acid used can be determined by the maximum level of diethylene glycol (DEG) that could be tolerated.
  • a CAMILETM system controlled conditions in the solid-staters - except for nitrogen flow rate, which was controlled manually with a rotameter. Heated nitrogen passed through a frit that supported a bed of precursor. The set point for the nitrogen temperature just below the frit was 205 °C, and the nitrogen flow rate was 14 standard cubic feet per hour.
  • Solid-stating rate studies were done in a random order different than that used for the melt-phase polymerizations. Prior to each solid-stating rate study, the standard particle size blend was thoroughly mixed, and then a 30-gram portion of the blend was removed and poured into a metal solid-stater. The bed was made level.
  • the acetaldehyde generation test was performed at 295°C. Ten grams of polymer were dried at 120°C overnight. The polymer was placed in a melt indexer for 5 minutes at 295°C, extruded and quenched. The polymer was cryogenically ground and sieved ( ⁇ 20 mesh particle size). An inert gas was passed across the sample (0.50 ⁇ 0.05 grams) at 150°C for 10 minutes. The gas was then sent to a trap cooled with liquid nitrogen. The trap was then heated to 300°C, and the acetaldehyde was swept into a gas chromatograph for measurement.
  • the solution haze was measured by dissolving the polymer (10.0 g) in a mixture of methylene chloride and hexafluoro isopropyl alcohol (130 mL, 70:30 v/v). The turbidity of the solution was measured with a Hach Ratio Nephelometric Turbidimeter. The mixtures were centrifuged to isolate the particulates when the solution haze values were > 5 ntu, except for Examples 13 and 15. The particulates were analyzed by x-ray diffraction (XRD) to identify crystalline species and by energy dispersive spectroscopy (EDS) to identify the elements, present, including those in amorphous species.
  • XRD x-ray diffraction
  • EDS energy dispersive spectroscopy
  • Example 13 Solid Stating of Polymer with 117 ppm of Antimony and 8 ppm of Phosphorus (Antimony Early/Phosphoric Acid Late)
  • Example 14 Solid Stating of Polymer with 140 ppm of Antimony and 48 ppm of Phosphorus (Antimony Early/Phosphoric Acid Late)
  • Example 15 Solid Stating of Polymer with 211 ppm of Antimony and 7 ppm of
  • Example 16 Solid Stating of Polymer with 223 ppm of Antimony and 50 ppm of Phosphorus (Antimony Early/Phosphoric Acid Late) Polymer was solid stated for 2 hours and 36 minutes. Analyses on the polymer resulted in the following data: IN of 0.686 dL/g, a L* color of 89.2, an a* color of- 1.0, a b* color of 3.9, an acetaldehyde generation at 295°C of 12.2 ppm, and a solution haze value of 6.8 ntu.
  • the particulates contained antimony oxide and antimony phosphate. EDS indicated that antimony and phosphates were present in the particulates.
  • Example 17 Solid Stating of Polymer with 8 ppm of Phosphorus and 122 ppm of Antimony (Antimony Late/Phosphoric Acid Early)
  • Example 18 Solid Stating of Polymer with 9 ppm of Phosphorus and 231 ppm of Antimony (Antimony Late/Phosphoric Acid Early)
  • Example 19 Solid Stating of Polymer with 43 ppm of Phosphorus and 123 ppm of Antimony (Antimony Late/Phosphoric Acid Early)
  • Example 20 Solid Stating of Polymer with 39 ppm of Antimony and 214 ppm of Phosphorus (Antimony Late/Phosphoric Acid Early)
  • Example 21 A Phosphate Triester as the Phosphorus Source
  • a phosphate triester like tri-t-butyl phosphate is the phosphorus source
  • the trends are different than those observed for phosphoric acid.
  • the antimony is added early and the phosphate triester is added late
  • the melt-phase finisher time is relatively insensitive to the phosphorus level.
  • the dramatic increase in finisher time with increasing phosphorus level for early antimony/late phosphoric acid addition is not seen when the phosphorus source is a phosphate triester.
  • antimony oxide alone is found in the particulates isolated from solution haze samples. In contrast to the situation with late addition of phosphoric acid, particulate haze from antimony phosphate is not a concern when a phosphate triester is added late.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de production de polyesters, notamment le polyéthylène téréphthalate (PET) impliquant une polymérisation, par exemple, une polycondensation d'au moins un diacide et d'au moins un diol en présence à la fois d'un catalyseur à base d'antimoine et d'un additif contenant du phosphore acide, par exemple du type acide phosphorique. L'additif contenant du phosphore acide est introduit avant le catalyseur à base d'antimoine, de préférence pendant une durée permettant une réaction entre ledit additif et au moins un diol présent dans le mélange de réaction. L'invention concerne également une résine de polyester produite à l'aide de ce procédé.
PCT/US1999/019385 1999-08-24 1999-08-24 Preparation de polyesters utilisant des catalyseurs a base d'antimoine et composes phosphores acides WO2001014452A1 (fr)

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Cited By (12)

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EP1281725A1 (fr) * 2001-01-25 2003-02-05 Mitsubishi Chemical Corporation Resine polyester, article moule a base de cette resine polyester et procede permettant de produire cette resine polyester
DE102009010597A1 (de) * 2008-07-12 2010-01-14 Epc Industrial Engineering Gmbh Verfahren zur Herstellung von Polyester, insbesondere linearer Polyester, für Textilgarne und Textilfasern sowie für Flaschen und Anlage zur Durchführung des Verfahrens
US7786247B2 (en) 2004-03-09 2010-08-31 Eastman Chemical Company High IV melt phase polyester polymer catalyzed with antimony containing compounds
CN102329420A (zh) * 2011-06-20 2012-01-25 江苏鹰翔化纤股份有限公司 1、2-丙二醇改性涤纶切片的制备方法
CN102964574A (zh) * 2012-12-07 2013-03-13 富维薄膜（山东）有限公司 改性聚酯及其制备方法
US8901272B2 (en) 2007-02-02 2014-12-02 Grupo Petrotemex, S.A. De C.V. Polyester polymers with low acetaldehyde generation rates and high vinyl ends concentration
US8968615B2 (en) 2004-09-02 2015-03-03 Eastman Chemical Company Low melting polyester polymers
US8987408B2 (en) 2005-06-16 2015-03-24 Grupo Petrotemex, S.A. De C.V. High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates
US9267007B2 (en) 2005-09-16 2016-02-23 Grupo Petrotemex, S.A. De C.V. Method for addition of additives into a polymer melt
WO2016091147A1 (fr) * 2014-12-11 2016-06-16 昆山天洋热熔胶有限公司 Colle thermofusible à base de polyester pour un revêtement en poudre et son procédé de préparation
US10208200B2 (en) 2017-03-30 2019-02-19 Graham Packaging Company, L.P. Dual oxygen-scavenging compositions requiring no induction period
US11345809B2 (en) 2014-11-07 2022-05-31 Graham Packaging Company, L.P. Oxygen scavenging compositions requiring no induction period

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1281725A4 (fr) * 2001-01-25 2005-04-06 Mitsubishi Chem Corp Resine polyester, article moule a base de cette resine polyester et procede permettant de produire cette resine polyester
US7048995B2 (en) 2001-01-25 2006-05-23 Mitsubishi Chemical Corporation Polyester resin, molded product made thereof and process for production of polyester resin
EP1281725A1 (fr) * 2001-01-25 2003-02-05 Mitsubishi Chemical Corporation Resine polyester, article moule a base de cette resine polyester et procede permettant de produire cette resine polyester
US7786247B2 (en) 2004-03-09 2010-08-31 Eastman Chemical Company High IV melt phase polyester polymer catalyzed with antimony containing compounds
US7902318B2 (en) 2004-03-09 2011-03-08 Eastman Chemical Company High IV melt phase polyester polymer catalyzed with antimony containing compounds
US8968615B2 (en) 2004-09-02 2015-03-03 Eastman Chemical Company Low melting polyester polymers
US8987408B2 (en) 2005-06-16 2015-03-24 Grupo Petrotemex, S.A. De C.V. High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates
US9267007B2 (en) 2005-09-16 2016-02-23 Grupo Petrotemex, S.A. De C.V. Method for addition of additives into a polymer melt
US8901272B2 (en) 2007-02-02 2014-12-02 Grupo Petrotemex, S.A. De C.V. Polyester polymers with low acetaldehyde generation rates and high vinyl ends concentration
DE102009010597A1 (de) * 2008-07-12 2010-01-14 Epc Industrial Engineering Gmbh Verfahren zur Herstellung von Polyester, insbesondere linearer Polyester, für Textilgarne und Textilfasern sowie für Flaschen und Anlage zur Durchführung des Verfahrens
CN102329420A (zh) * 2011-06-20 2012-01-25 江苏鹰翔化纤股份有限公司 1、2-丙二醇改性涤纶切片的制备方法
CN102964574A (zh) * 2012-12-07 2013-03-13 富维薄膜（山东）有限公司 改性聚酯及其制备方法
US11345809B2 (en) 2014-11-07 2022-05-31 Graham Packaging Company, L.P. Oxygen scavenging compositions requiring no induction period
WO2016091147A1 (fr) * 2014-12-11 2016-06-16 昆山天洋热熔胶有限公司 Colle thermofusible à base de polyester pour un revêtement en poudre et son procédé de préparation
US10208200B2 (en) 2017-03-30 2019-02-19 Graham Packaging Company, L.P. Dual oxygen-scavenging compositions requiring no induction period

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