WO2016126757A1 - Procédés de préparation d'un oligomère de polyester macrocyclique à partir d'un polyester linéaire - Google Patents

Procédés de préparation d'un oligomère de polyester macrocyclique à partir d'un polyester linéaire Download PDF

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WO2016126757A1
WO2016126757A1 PCT/US2016/016268 US2016016268W WO2016126757A1 WO 2016126757 A1 WO2016126757 A1 WO 2016126757A1 US 2016016268 W US2016016268 W US 2016016268W WO 2016126757 A1 WO2016126757 A1 WO 2016126757A1
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catalyst
mixture
terephthalate
mpo
solid
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PCT/US2016/016268
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English (en)
Inventor
James MIHALICH
Jimmy Lynn Webb
John LIPPERT, III
Lori C. BURRY
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Liquid Thermo Plastics, Inc.
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Publication of WO2016126757A1 publication Critical patent/WO2016126757A1/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
    • C08G63/02—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
    • 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
    • C08G63/81—Preparation processes using solvents
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material

Definitions

  • This invention relates generally to methods for preparing macrocyclic polyester oligomer (MPO). More particularly, in certain embodiments, the invention relates to methods for preparing macrocyclic polyester oligomer from linear polyester.
  • MPOs Macrocyclic polyester oligomers
  • MPOs have unique properties that make them attractive as matrix-forming resins for engineering thermoplastic composites.
  • MPOs lend valuable characteristics to polymerized products, for example, high strength, high gloss, and solvent resistance.
  • certain MPOs melt and polymerize at temperatures well below the melting point of the resulting polymer, polymerization and crystallization can occur virtually isothermally upon melting of the MPO in the presence of an appropriate catalyst.
  • the time and expense required to thermally cycle a tool is favorably reduced, because demolding can take place immediately following polymerization, without first cooling the mold.
  • polybutylene terephthalate (PBT) and other polyalkylene terephthalates may be depolymerized to form macrocyclic polyester oligomers (MPOs), including, for example, the cyclic form of poly(l,4-butylene terephthalate) (cPBT).
  • PBT polybutylene terephthalate
  • MPOs macrocyclic polyester oligomers
  • cPBT poly(l,4-butylene terephthalate)
  • the depolymerization reaction is an equilibrium reaction that progresses relatively slowly and produces undesired byproducts, including hydroxybutylester linear oligomers (referred to herein as "linears"), which must be separated from the product stream, or recycled. These byproducts are typically gellular in nature, and are physically difficult to filter or otherwise remove from solution. Furthermore, the above depolymerization methods require precipitation and removal of catalyst residue from the reaction solution. Many downstream applications of MPOs are intolerant of residual catalyst and/or metal(s) used in catalysts during MPO manufacturing, including manufacturing of linear polyester precursors. The separation, extraction, and/or recycle of linears and/or catalyst residue necessitate added process steps and unit operations in the manufacture of MPOs, thereby increasing both capital expense and operating costs.
  • MPOs Currently, the production of MPOs currently involves the reaction of terephthalate (e.g., dimethyl terephthalate) with a diol in a solvent with concomitant removal of transesterification byproducts (e.g., methanol and water).
  • terephthalate e.g., dimethyl terephthalate
  • transesterification byproducts e.g., methanol and water
  • solvent dilutes the concentration of the solution and makes it difficult and costly to remove byproducts such as methanol.
  • the presence of methanol in the reaction mixture makes the transesterification reaction less efficient due to the fact that methanol is in equilibrium with the diol.
  • the invention relates to methods and systems for preparing macrocyclic polyester oligomer (MPO) from a linear polyester composition.
  • MPO is produced starting from monomers comprising a diol and a terephthalate or a precursor thereof, forming a linear polyester in situ which is then cyclized to form MPO.
  • MPO is produced by first depolymerizing a linear polyester into shorter oligomers and then cyclizing to form MPO.
  • the step of cyclizing to form MPO comprises heterogeneous catalysis.
  • the present invention relates to, among other things, methods for making MPO utilizing a two-step process wherein i) a linear polyester composition resulting from transesterification of a terephthalate and diol is made without a solvent and ii) the linear polyester composition is then cyclized in the presence of a solvent and heterogenous catalyst to make MPO.
  • cyclic poly(butylene terephthalate) is prepared via heterogeneous catalysis by reacting a linear polyester composition (e.g., from a transesterification or depolymerization reaction) in the presence of a heterogenous titanium catalyst in an organic solvent - for example, xylene.
  • the reactants come into contact with the catalyst-containing solid, for example, titanium catalyst-coated glass beads, titanium catalyst- coated fiberglass, titanium catalyst-coated silica gel, or titanium catalyst-adhered magnetic iron oxide.
  • the catalyst-containing solid may be packed in a column or bed, or may be loose in the reaction vessel.
  • MPO is produced in the reaction mixture, while residual linears and catalyst residue remain in the column/bed of fiberglass or silica gel, thereby obviating or at least reducing the filtration required for separating out the MPO produced.
  • the invention relates to a method for preparing a MPO, the method comprising: (i) heating a mixture, the mixture comprising a diol and a terephthalate or a precursor thereof, thereby producing a linear polyester composition; (ii) adding an organic solvent to the mixture; and (iii) contacting the mixture with a solid comprising a catalyst, thereby producing MPO.
  • the invention relates to (i) providing a linear polyester composition comprising diol and terephthalic acid monomers; (ii) adding an organic solvent to the polyester composition; (iii) heating the resulting mixture; and (iv) contacting the mixture with a solid comprising a catalyst, thereby producing MPO.
  • the provided linear polyester composition is substantially free of methanol and water.
  • step (i) comprises depolymerizing a polyester.
  • the depolymerization comprises contacting polyester with a solid comprising a catalyst in the presence of an organic solvent and heating the resulting mixture.
  • step (i) comprises heating a mixture, the mixture comprising a diol, a terephthalate or a precursor thereof, and optionally a solid comprising a catalyst, thereby producing a linear polyester composition.
  • no solvent is added prior to the step of contacting the mixture with a solid comprising a catalyst to form MPO.
  • the MPO produced may be cPBT, cPPT, cPCT, cPET, cPEN, and/or copolymer oligomers thereof.
  • the method may further include the step of collecting the MPO.
  • the collected MPO is at least 80 wt.% dimer, trimer, tetramer, and/or pentamer species.
  • the yield of MPO is at least 35%, at least 40%, at least 45%, or at least 50%.
  • a recycle stream may be used to improve yield.
  • Figure 1 is a schematic drawing of a microplant for the production MPO from a linear polyester composition comprising diol and terephthalic acid monomers.
  • compositions, mixtures, blends, and composites are described as having, including, or comprising specific components, or where processes and methods are described as having, including, or comprising specific steps, it is contemplated that, additionally, there are compositions, mixtures, blends, and composites of the present invention that consist essentially of, or consist of, the recited components, and that there are processes and methods of the present invention that consist essentially of, or consist of, the recited processing steps.
  • the present invention encompasses the recognition that conventional techniques of making MPO that employ solvent at the transesterification step suffer inefficiencies in the removal of transesterification byproducts methanol and/or water at low concentration.
  • the present invention provides, among other things, methods for making MPO utilizing a two-step process wherein i) a linear polyester composition resulting from transesterification of a terephthalate and diol is made without a solvent and ii) the linear polyester composition is then cyclized in the presence of a solvent and heterogenous catalyst to make MPO.
  • Such methods offer the advantage of being able to more easily remove transesterification byproducts (such as methanol and water) at high concentration.
  • the use of a heterogenous catalyst facilitates easy and complete separation of catalyst from reaction product.
  • the present invention further encompasses the recognition that commercial sources of linear polyester contains a residual amount of catalyst that can complicate the production of MPO and certain downstream applications of MPOs. For example, it has been observed that the addition of diol to certain sources of commercial polyester can cause the formation of MPO (i.e., without the addition of catalyst).
  • the present invention includes the previously unknown source of a problem.
  • the present invention addresses the recognition of this problem by, in some embodiments, providing methods which form a linear polyester from a diol and a terephthalate or a precursor thereof.
  • the present invention also addresses the recognition of this problem by, in some embodiments, providing methods which utilize a heterogenous catalyst (e.g., a solid comprising a catalyst) for the production of MPO.
  • a heterogenous catalyst e.g., a solid comprising a catalyst
  • the invention relates to (i) providing a linear polyester composition comprising diol and terephthalic acid monomers; (ii) adding an organic solvent to the polyester composition; (iii) heating the resulting mixture; and (iv) contacting the mixture with a solid comprising a catalyst, thereby producing MPO.
  • the provided linear polyester composition is substantially free of methanol and water.
  • step (i) comprises depolymerizing a polyester.
  • the depolymerization comprises contacting polyester with a solid comprising a catalyst in the presence of an organic solvent and heating the resulting mixture.
  • step (i) comprises heating a mixture, the mixture comprising a diol, a terephthalate or a precursor thereof, and optionally a solid comprising a catalyst, thereby producing a linear polyester composition.
  • step (i) is performed in the absence of a solvent other than the reacting constituents.
  • a solvent used in step (i) is present in an amount less than about 1000: 1, about 500: 1, about 200: 1, about 100: 1, about 10: 1, about 5: 1, about 1 : 1, about 0.5: 1, about 0.1 : 1, or about 0:01 : 1 of solvent to other components.
  • a provided linear polyester composition is substantially free of methanol and water.
  • step (i) comprises depolymerizing a polyester.
  • the depolymerization comprises contacting polyester with a solid comprising a catalyst in the presence of an organic solvent and heating the resulting mixture.
  • steps (i)-(iv) of the method described in the previous paragraph are performed simultaneously.
  • the invention relates to a method for preparing a MPO, the method comprising: (i) heating a mixture, the mixture comprising a diol and a terephthalate or a precursor thereof, thereby producing a linear polyester composition; (ii) adding an organic solvent to the mixture; and (iii) contacting the mixture with a solid comprising a catalyst, thereby producing MPO.
  • the transesterification reaction of a diol and a terephthalate is performed in the absence of a catalyst.
  • step (i) is performed in the absence of a solvent other than the reacting constituents.
  • a solvent used in step (i) is present in an amount less than about 1000: 1, about 500: 1, about 200: 1, about 100: 1, about 10: 1, about 5: 1, about 1 : 1, about 0.5: 1, about 0.1 : 1, or about 0:01 : 1 of solvent to other components.
  • a linear polyester composition is substantially linear oligomers. In some embodiments of the provided methods, a linear polyester composition is substantially linear oligomers having between 2 and 20 repeating units, inclusive. In some embodiments, a linear polyester composition is substantially linear oligomers having between 10 and 20 repeating units, inclusive.
  • the terms "repeating unit” or “repeat unit” refer to a polyester repeating unit (e.g., a diol -terephthalate unit).
  • OH end group refers to a hydroxyl group and not a carboxyl group.
  • a provided linear polyester composition has greater than about 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 97%, 98%, 99%, 99.5%, or 99.9% OH end groups.
  • a linear polyester composition is the output of an esterifaction reaction from a linear polyester production stream.
  • such linear polyesters are selected from the group consisting of PBT, PPT, PCT, PET, PEN, or PTT.
  • a terephthalate is a diester of terephthalic acid.
  • a diester is dimethyl terephthalate, diisopropyl terephthalate, diphenyl terephthalate, butanediol terephthalate, or a combination thereof.
  • a diester is dimethyl terephthalate.
  • a reaction mixture comprises a precursor of terephthalate, wherein the precursor is terephthalic acid.
  • embodiments of the invention that employ DMT may alternatively employ PTA (purified or non- purified forms), for example, where DMT is formed from PTA.
  • PTA purified or non- purified forms
  • DMT is formed from PTA.
  • the use of known chemical analogues and/or precursors of species described herein are considered to lie within the scope of the invention.
  • the method further comprises removing alcohol produced from a transesterification reaction.
  • an alcohol is methanol.
  • the method further comprises removing water produced.
  • the heating step and contacting steps are performed at the same time.
  • the solid comprising the catalyst is contacted with the mixture subsequent to or concomitantly with the addition of organic solvent.
  • a contacting step is performed in the presence of heat.
  • the method further comprises collecting the MPO.
  • Macrocyclic polyester oligomers that may be employed and made in this invention include, but are not limited to, macrocyclic poly(alkylene dicarboxylate) oligomers having a structural repeat unit of the formula:
  • A is an alkylene, or a cycloalkylene or a mono- or polyoxyalkylene group; and B is a divalent aromatic or alicyclic group.
  • Preferred macrocyclic polyester oligomers include macrocyclic poly(l,4-butylene terephthalate) (cPBT), macrocyclic poly(l,3-propylene terephthalate) (cPPT), macrocyclic poly(l,4-cyclohexylenedimethylene terephthalate) (cPCT), macrocyclic poly(ethylene terephthalate) (cPET), macrocyclic polytrimethylene terephthalate PTT (cPTT), and macrocyclic poly(l,2-ethylene 2,6-naphthalenedicarboxylate) (cPEN) oligomers, and copolyester oligomers comprising two or more of the above repeating units.
  • an MPO is cPBT.
  • macrocyclic ester homo- and co-oligomers produced via methods of this invention include oligomers having a general structural repeat unit of the formula:
  • A' is an alkylene, cycloalkylene, or mono- or polyoxyalkylene group, and where A' may be substituted, unsubstituted, branched, and/or linear.
  • Example MPOs of this type include butyrolactone and caprolactone, where the degree of polymerization is one, and 2, 5-dioxo-l,4- dioxane, and lactide, where degree of polymerization is two. The degree of polymerization may also be 3, 4, 5, or higher. Molecular structures of 2, 5-dioxo-l,4-dioxane and lactide,
  • a macrocyclic polyester oligomer (an MPO) produced via methods of the invention includes species of different degrees of polymerization, although, in certain embodiments, MPO with a high concentration of a particular species may be produced.
  • a degree of polymerization (DP) with respect to the MPO means the number of identifiable structural repeat units in the oligomeric backbone.
  • the structural repeat units may have the same or different molecular structure.
  • an MPO may include dimer, trimer, tetramer, pentamer, and/or other species.
  • the MPO is primarily (e.g., consists essentially of) dimer, trimer, tetramer, and/or pentamer species.
  • the MPO is primarily (e.g., consists essentially of) trimer, tetramer, and/or pentamer species (e.g., C3+C4+C5).
  • a dialkyl terephthalate such as DMT
  • those methods are also contemplated to include variations of the method in which terephthalic acid (TP A) is used instead of at least a portion of the dialkyl terephthalate.
  • TP A terephthalic acid
  • a method of the invention in which a reaction is performed using a dialkyl terephthalate and a diol inherently includes an adaptation in which terephthalic acid is used instead of (or in addition to) dialkyl terephthalate.
  • the invention includes pilot plant and plant-scale manufacturing processes whose feasibility is demonstrated by the laboratory-scale experiments described herein.
  • the chemical reactions described herein may be performed using reactor equipment that is known to those of ordinary skill in the field of polymer manufacturing and processing, including, without limitation, for example, batch reactors, plug-flow reactors, continuously-stirred tank reactors, packed-bed reactors, slurry reactors, fluidized bed reactors, and columns. Chemical reactions described herein may be conducted in batch, semi-continuous, and/or continuous operation.
  • Scale-up of systems from laboratory to plant scale may be performed by those of ordinary skill in the field of polymer manufacturing and processing.
  • those of ordinary skill in this field may select reactor types, design experiments for obtaining kinetic data, develop and apply models for reactor design, develop economically optimum reactor design, and/or validate reactor designs via pilot plant and/or full scale reactor experiments.
  • General information regarding reactors and the design of reactor systems for manufacture of products may be found, for example, in "Kinetics and Reaction Engineering," John L. Falconer, editor, in The Engineering Handbook, Section X, Richard C. Dorf, editor-in-chief, CRC Press, Inc., ISBN 0-8493-8344-7, pp. 785-829 (1995).
  • Any suitable techniques for material separation, isolation, and purification may be adapted for application in manufacturing processes encompassed by various embodiments of the invention, for example, techniques for distillation, extraction, reactive extraction, adsorption, absorption, stripping, crystallization, evaporation, sublimation, diffusional separation, adsorptive bubble separation, membrane separation, and/or fluid-particle separation.
  • separation processes and their design may be found, for example, in "Separation Processes,” Klaus Timmerhaus, editor, in The Engineering Handbook, Section VIII, Richard C. Dorf, editor-in-chief, CRC Press, Inc., ISBN 0-8493-8344-7, pp. 579-657 (1995).
  • methods, systems, and processes of the claimed invention may include pumps, heat exchangers, and gas-, liquid-, and/or solid-phase material handling equipment known to those of ordinary skill in the field of polymer manufacturing and processing.
  • Embodiments of the invention may be performed as part of a continuous, semi- continuous, or batch process.
  • Reactors may be single-stage or multi-stage. It is contemplated that methods of the invention may be combined or supplemented with reactors, systems, or processes that are known in the art.
  • macrocyclic is understood to mean a cyclic molecule having at least one ring within its molecular structure that contains 5 or more atoms covalently connected to form the ring.
  • an "oligomer” is understood to mean a molecule that contains one or more identifiable structural repeat units of the same or different formula.
  • macrocyclic polyester oligomer (MPO), or “cyclics”, is understood to mean macrocyclic oligomer containing structural repeat units having an ester functionality.
  • a macrocyclic polyester oligomer typically refers to multiple molecules of one specific repeat unit formula. However, a macrocyclic polyester oligomer also may include multiple molecules of different or mixed formulae having varying numbers of the same or different structural repeat units.
  • the terms “macrocyclic polyester oligomer” and “macrocyclic polyester oligomers” may be used interchangeably.
  • the terms “macrocyclic polyester oligomer” and “macrocyclic oligoester” are used interchangeably herein.
  • a macrocyclic polyester oligomer may be a co-polyester or multi-component polyester oligomer, i.e., an oligomer having two or more different structural repeat units having ester functionality within one cyclic molecule.
  • substantially free of means that the composition contains no significant amount of the matter from which it is stated to be substantially free of (e.g., water and/or methanol). In some embodiments, a composition has less than about 20%, 10%, 5%, 2%, 1%), 0.5%), 0.1%), or 0.01%) of matter from which it is stated to be substantially free of.
  • the organic solvent includes at least one member selected from the group consisting of tetradecane, hexadecane, octadecane, toluene, xylene, trimethylbenzene, tetramethylbenzene, ethylbenzene, propylbenzene, naphthalene, methylnaphthalene, biphenyl, triphenyl, diphyenyl ether (or a halogenated derivative thereof), anisol, methylene chloride, dimethyoxybenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, dichloronaphthalene, and/or a perfluorocarbon.
  • the organic solvent comprises a high-purity hydrocarbon solvent (e.g., Drakesol 165 (e.g., manufactured by Orica Chemicals), composed of acid treated light petroleum distillates).
  • the organic solvent comprises one or more components selected from the group consisting of oDCB (ortho-dichlorobenzene), toluene, o- xylene, pyridine, triethylamine, heptane, dibutyl ether, decane, and trichlorobenzene (TCB).
  • oDCB ortho-dichlorobenzene
  • toluene o- xylene
  • pyridine triethylamine
  • heptane heptane
  • dibutyl ether dibutyl ether
  • decane trichlorobenzene
  • TCB trichlorobenzene
  • the organic solvent is or comprises xylene.
  • the organic solvent includes a perfluorocompound, such as perfluoro(tri-n-butylamine) and perfluoro(tri-n-pentylamine).
  • the organic solvent used preferably has a boiling point no less than about 110 °C.
  • solvent refers to solvents that are added to the reaction mixture, but does not include substances that may become part of a reaction mixture as a byproduct of a reaction described herein.
  • Suitable catalysts that may be used to practice the present invention include, but are not limited to, various organotitanate and organotin compounds.
  • the catalyst is a heterogeneous catalyst derived from an organotitanate or organotin compound.
  • the catalyst is or is derived from at least one member selected from the group consisting of 2-ethylhexyl titanate, tetrakis-(2-ethylhexyl) titanate, tetrabutyl titanate, tetraisopropyl titanate, an alkoxy titanate, titanium methoxide, titanium ethoxide, diisopropoxide bis(2,4-pentanedionate), triethanolamine titanium in alcohol solvent, and butanediol titanate, or a heterogeneous derivative thereof.
  • the catalyst is or is derived from tetraisopropyl titanate.
  • a solid comprising a catalyst is a member selected from the group comprising titanium catalyst-coated glass beads, titanium catalyst-coated fiberglass, titanium catalyst-coated silica gel, titanium catalyst-coated melamine formaldehyde solids (e.g., solids, beads, etc.), and titanium catalyst-adhered magnetic iron oxide.
  • a solid comprising a catalyst is titanium catalyst-coated glass beads.
  • a solid comprising a catalyst is titanium catalyst-coated glass beads pretreated with diol.
  • a solid comprising a catalyst is titanium catalyst-coated glass beads pretreated with 1,4-butanediol.
  • the method makes use of glass beads coated with a titanium catalyst, over which a reaction solution passes.
  • catalyst-coated silica gel may be used, or another catalyst-coated (or otherwise catalyst-containing) solid, e.g., in a packed bed or column, may be used.
  • the result is a much simpler, more efficient method of manufacturing MPOs that produces a substantially pure MPO product stream, where linear byproducts and catalyst residue are trapped on/in the solid (e.g., in the packed bed or column).
  • Embodiments of the invention also offer the ability to use lower catalyst concentrations in the preparation of cPBT and other MPOs.
  • the use of less catalyst offers a cost savings, as well as other benefits.
  • the use of lower catalyst concentrations may lower the amount of residual oligomers (i.e. non-MPO, hydroxyl- and/or acid-capped linears) formed and improve efficiency of MPO production. This may result in a lower level of residual acids in the column, and the period of time in which column packing becomes spent and needs to be replaced or recycled is longer.
  • the residual oligomer filtrate may be less gellular and easier to remove from the column
  • the reaction mixture comprises a diol.
  • Suitable diols include but are not limited to: polyethylene glycol, polypropylene glycol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-l,3-diol, 2-butyl-2- ethylpropane-l,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1, 10-decanediol, 1,12- dodecanediol, 2,2,4,4-tetramethylcyclobutane-l,3-diol, 1,3-cyclopen
  • the diol is polyethylene glycol. In some embodiments, the diol is butanediol. In some embodiments, the diol is 1,4-butanediol. [0053] In some embodiments of the methods and processes described herein, the reaction mixture comprises a phenol. In certain embodiments, the phenol is resorcinol. In other embodiments, the phenol is hydroquinone.
  • the terephthalate is dimethyl terephthalate (DMT). In some embodiments, the terephthalate is diphenyl terephthalate (DPT). In some embodiments, the terephthalate is diisopropyl terephthalate or bis- hydroxylethylene terephthalate (BHET).
  • DMT dimethyl terephthalate
  • DPT diphenyl terephthalate
  • BHET bis- hydroxylethylene terephthalate
  • BDO and terephthalic acid undergo esterification in an esterification reactor, wherein BDO, H 2 0, and THF are distilled off and BDO recycled back into the reactor.
  • a linear polymer stream is directed to a mix tank, wherein xylene is added and the resulting mixture is directed to a cyclizing reactor.
  • Cyclization of linears to MPO proceeds in the cyclizing reactor, and a MPO product stream is removed.
  • MPO product removal and isolation comprises filtration of linears (and recycling of the same to the mix tank), and solvent stripping (and recycling of the same to the mix tank).
  • polymer products obtained from these examples may be confirmed by conventional techniques such as high performance liquid chromatography (HPLC) and gel permeation chromatography (GPC).
  • HPLC high performance liquid chromatography
  • GPC gel permeation chromatography
  • terephthalic acid (TA) (50.05 g, 0.301 mol) and 1,4-butanediol (265 mL, 2.99 mol).
  • TA terephthalic acid
  • 1,4-butanediol (265 mL, 2.99 mol).
  • the mixture was heated to 230 °C under a nitrogen atmosphere.
  • the THF/H 2 0 (73.5 g) produced by the reaction was captured overhead.
  • the excess BDO (152 g) was then removed via vacuum distillation at ⁇ 5 mmHg.
  • GPC chromatogram of the product indicates linears (indicated as a molecular weight inclusive of a BT heptamer and beyond, wherein each B is a unit of BDO and each T is a unit of TA) present as 52% of the complete chromatogram.
  • the BDO pretreated glass bead catalyst was then poured into a cellulose extraction thimble and subjected to Soxhlet Extraction with xylene (500 mL) for 60 minutes. The material was finally dried in a vacuum oven at 150 °C prior to use in Example 3.
  • terephthalic acid 1,4-butanediol
  • catalyst 1,4-butanediol
  • the mixture was heated to 220 °C in an oil bath under N 2 and monitored by HPLC and GPC chromatography.
  • GPC linears refers to the integration of the GPC spectrum inclusive of the heptamer (C7) and beyond.
  • TA refers to terephthalic acid.
  • BDO refers to 1,4- butanediol.
  • TiB 2 and T 2 B 3 both refer to intermediate diols that are seen in the HPLC, wherein TiB 2 represents B-T-B with each B as a unit of BDO and each T as a unit of TA, and wherein T 2 B 3 represents B-T-B-T-B.
  • the percentages in the table for these diols depict the relative amounts of these intermediates at the given time point in relation to the full chromatogram.
  • GPC linears refers to the integration of the GPC spectrum inclusive of the heptamer (C7) and beyond.
  • TA refers to terephthalic acid.
  • BDO refers to 1,4-butanediol.
  • TiB 2 and T 2 B 3 both refer to intermediate diols that are seen in the HPLC. The percentages in the table for these diols depict the relative amounts of these intermediates at the given time point in relation to the full chromatogram.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne des procédés de préparation d'un oligomère de polyester macrocyclique (MPO). Elle concerne plus particulièrement des procédés pour la préparation d'un oligomère de polyester macrocyclique à partir de polyester linéaire.
PCT/US2016/016268 2015-02-05 2016-02-03 Procédés de préparation d'un oligomère de polyester macrocyclique à partir d'un polyester linéaire WO2016126757A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5407984A (en) * 1994-08-31 1995-04-18 General Electric Company Process for preparing macrocyclic polyester oligomers
US7732557B2 (en) * 2005-03-25 2010-06-08 Cyclics Corporation Methods for removing catalyst residue from a depolymerization process stream
US20120302721A1 (en) * 2011-02-23 2012-11-29 Jimmy Lynn Webb Methods for Preparation of Macrocyclic Polyester Oligomer via Heterogeneous Catalysis

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5407984A (en) * 1994-08-31 1995-04-18 General Electric Company Process for preparing macrocyclic polyester oligomers
US7732557B2 (en) * 2005-03-25 2010-06-08 Cyclics Corporation Methods for removing catalyst residue from a depolymerization process stream
US20120302721A1 (en) * 2011-02-23 2012-11-29 Jimmy Lynn Webb Methods for Preparation of Macrocyclic Polyester Oligomer via Heterogeneous Catalysis

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"The Engineering Handbook", 1995, CRC PRESS, INC., article "Kinetics and Reaction Engineering", pages: 785 - 829
"The Engineering Handbook", 1995, CRC PRESS, INC., article "Separation Processes", pages: 579 - 657

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