WO2014160317A1 - Procédés de préparation d'oligomère de polyester par catalyse basique - Google Patents

Procédés de préparation d'oligomère de polyester par catalyse basique Download PDF

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Publication number
WO2014160317A1
WO2014160317A1 PCT/US2014/026311 US2014026311W WO2014160317A1 WO 2014160317 A1 WO2014160317 A1 WO 2014160317A1 US 2014026311 W US2014026311 W US 2014026311W WO 2014160317 A1 WO2014160317 A1 WO 2014160317A1
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Prior art keywords
mpo
reaction mixture
terephthalate
ester
base catalyst
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PCT/US2014/026311
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English (en)
Inventor
Jimmy Lynn Webb
III John LIPPERT
James MIHALICH
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Liquid Thermo Plastics, Inc.
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Publication of WO2014160317A1 publication Critical patent/WO2014160317A1/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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, 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

  • 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 using a base catalyst.
  • 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.
  • Various methods for preparing MPO by depolymerizing polyesters have been described.
  • 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).
  • 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.
  • linears hydroxybutylester linear oligomers
  • These byproducts are typically gellular in nature, and are physically difficult to filter or otherwise remove from solution.
  • depolymerization methods require precipitation and removal of catalyst residue from the reaction solution.
  • 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.
  • MPO macrocyclic polyester oligomer
  • metal alkoxides such as sodium methoxide or potassium methoxide are found as effective base catalysts in the production of cyclic esters from diols and di-esters.
  • the potential for production of THF from diol side reactions is reduced in comparison to the use of acidic or neutral catalysts such as organo-titanates, for example.
  • organic bases such as triazabicyclodecene (TBD) are found to be particularly efficient catalysts, in that they appear to allow short oligomer to grow on the catalyst, and MPO is 'spun off the catalyst. Lower amounts of catalyst are needed, and the potential for furan or acetaldehyde production is low.
  • TBD triazabicyclodecene
  • a phenol di-ester such as diphenyl terephthalate (DPT) in the transesterification eliminates or reduces methano lysis.
  • DPT diphenyl terephthalate
  • an initial stage may involve reacting terephthalic acid and phenol in an esterification reactor to produce DPT, which is fed into a transesterification reactor in which the base-catalyzed production of MPO described herein takes place. Phenol is evolved and fed back into the esterification reactor.
  • MPO is prepared by a method comprising the steps of (a) heating a reaction mixture comprising (i) an alcohol, phenol, or both; (ii) a terephthalate di-ester (e.g., DMT or DPT) or, alternatively or additionally, a terephthalate precursor (e.g., TP A); (iii) a base (e.g., an organic base); and (iv) an organic solvent (different from the species in (i), (ii), and (iii) above), thereby forming MPO and polyester linears; and (b) separating the MPO from the reaction mixture.
  • a reaction mixture comprising (i) an alcohol, phenol, or both; (ii) a terephthalate di-ester (e.g., DMT or DPT) or, alternatively or additionally, a terephthalate precursor (e.g., TP A); (iii) a base (e.g., an organic base); and (iv)
  • the MPO precipitates (e.g., crystallizes) out of the reaction mixture at a different temperature than the polyester linears
  • the step (b) of separating the MPO comprises maintaining the reaction mixture within a temperature range in which the polyester linears substantially precipitate out of the reaction mixture (e.g., at least about 80 wt.% of the polyester linears in solution precipitate out), but in which the MPO substantially does not precipitate out of the reaction mixture (e.g., at least about 80 wt.% of the MPO in solution stays in solution).
  • a substantial portion of the base associates with
  • step (b) comprises maintaining the reaction mixture temperature within a temperature range such that the polyester linears with the substantial portion of the base associated therewith
  • At least a portion of the base from the reaction mixture of step (a) precipitates out of the reaction mixture with at least a portion of the polyester linears formed, and at least a portion of the precipitated base is recovered and returned to the reaction mixture in step (a) for further use.
  • the method comprises contacting a melt blend with one or more other components of the reaction mixture, wherein the melt blend comprises at least one of (A) terephthalic acid and isophthalic acid, and at least one of (B) hydroquinone and resorcinol.
  • the method further comprises contacting terephthalic acid (TP A) and a single functional alcohol to produce a terephthalate di-ester that is then used in the reaction mixture of step (a).
  • a single functional alcohol is an aromatic alcohol.
  • a single functional aromatic alcohol is phenol and the terephthalate di-ester is DPT.
  • the single functional aromatic alcohol is cresol.
  • the di-ester is dialkyl terephthalate. In some embodiments, a di-ester is dimethyl terephthalate (DMT). In some embodiments, the step of contacting TPA and the single functional aromatic alcohol is performed at a temperature of at least 180 °C (e.g., about 300 °C). In some embodiments, the step of contacting TPA and the single functional aromatic alcohol is performed at a temperature of between about 230 °C and about 260 °C.
  • the reaction mixture in step (a) is maintained at a solids content of no greater than about 5 wt.% solids (e.g., 1 wt.% solids).
  • reaction mixtures in step (a) occurs in an esterification reactor.
  • the present invention provides a process for preparing a
  • MPO the process comprising: (a) contacting terephthalic acid (TPA) and a single functional alcohol in an esterification reactor to produce a di-ester (e.g., DPT); (b) contacting the di-ester with a diol and a base catalyst in an organic solvent in a trans- esterification reactor, thereby forming MPO and polyester linears; and (c) removing and isolating the formed MPO.
  • TPA terephthalic acid
  • DPT di-ester
  • a diol and a base catalyst in an organic solvent in a trans- esterification reactor, thereby forming MPO and polyester linears
  • removing and isolating may be done by a variety of techniques (e.g. liquid-liquid extraction, filtering, heat exchangers), including those described below.
  • a single functional alcohol is an aromatic alcohol.
  • a single functional aromatic alcohol is phenol and the di-ester is DPT.
  • the single functional aromatic alcohol is cresol.
  • a di-ester is dialkyl terephthalate. In some embodiments, a di-ester is dimethyl terephthalate (DMT).
  • the process comprises selectively precipitating out of solution the polyester linears formed in the trans-esterification reactor (e.g., the MPO stays in solution and does not precipitate out of solution at the temperature at which polyester linears begin to precipitate out), wherein at least a portion of the base catalyst is associated with the polyester linears and precipitates out of solution with the polyester linears.
  • the process comprises precipitating out of solution the MPO formed in the trans-esterification reactor following precipitation of the polyester linears out of solution.
  • the process further comprises isolating at least a portion of the base catalyst after it precipitates out of solution with the polyester linears and is removed from the trans-esterification reactor, and returning the portion of the base catalyst to the trans-esterification reactor (e.g., the recycled base catalyst substantially free of the polyester linears).
  • the present invention relates to methods and systems for preparing linear polyester oligomer.
  • the methods and systems for making such oligomers are similar to the methods and systems for making MPO, with the exception that the organic solvent is omitted.
  • the present invention provides a method for preparing a polyester via base-mediated organic reaction, the method comprising heating a reaction mixture, the reaction mixture comprising (i) an alcohol, phenol, or both; (ii) a phenol di-ester (e.g., DPT); and (iii) a base catalyst (e.g., an organic base), thereby forming a polyester.
  • the reaction mixture comprises a substituted or unsubstituted aromatic alcohol (e.g., a substituted phenol such as cresol).
  • the present invention provides a process for preparing polyester via base-mediated organic reaction, the process comprising (a) contacting terephthalic acid (TPA) and a single functional alcohol in an esterification reactor to produce a di-ester (e.g., DPT); and (b) contacting the di-ester with a diol and a base catalyst in a trans-esterification reactor, thereby forming polyester.
  • TPA terephthalic acid
  • DPT di-ester
  • the single function alcohol is an aromatic alcohol.
  • the single functional aromatic alcohol is phenol and the di-ester is diphenyl terephthalate (DPT).
  • the process further comprises performing a polycondensation reaction with polyester formed in a trans-esterification reactor, thereby increasing molecular weight of the polyester.
  • step (a) comprises heating a melt blend comprising at least one of (i) terephthalic acid and isophthalic acid, and at least one of (ii) hydroquinone and resorcinol.
  • the content of the esterification reactor is maintained at a temperature of at least 180 °C (e.g., about 300 °C).
  • the content of the trans-esterification reactor is maintained at a temperature of between about 230 °C and about 260 °C.
  • the di-ester is dimethyl terephthalate (DMT).
  • the base catalyst is or comprises an organic base. In some embodiments, the base catalyst is an amine base. In some embodiments, the base catalyst is or comprises
  • the base catalyst is or comprises one or both of sodium alkoxide (e.g., sodium methoxide) and potassium alkoxide (e.g., potassium methoxide).
  • the reaction mixture comprises a diol.
  • Suitable diols include but are not limited to:
  • the reaction mixture comprises a phenol.
  • the phenol is resorcinol.
  • the phenol is hydroquinone.
  • the terephthalate is dimethyl terephthalate (DMT). In some embodiments, the terephthalate is diphenyl terephthalate (DPT).
  • 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 e.g., o-xylene
  • pyridine triethylamine
  • heptane heptane
  • dibutyl ether dibutyl ether
  • decane trichlorobenzene
  • TCB trichlorobenzene
  • the organic solvent is toluene.
  • no catalyst is used other than the base (e.g., the reaction is a base-mediated organic reaction). In some embodiments, no catalyst is used in the trans-esterification reactor other than the base (e.g., the trans-esterification reaction is base-mediated).
  • 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.
  • 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 20%, 30% 35%, at least 40%, at least 45%, or at least 50%.
  • a recycle stream may be used to improve yield.
  • Linear polyesters may be produced as well, including but not limited to
  • the polyester is PBT.
  • an organic solvent comprises toluene.
  • Suitable base catalysts that may be used to practice the present invention include, but are not limited to, various organic and inorganic bases. In some
  • a base catalyst is a metal alkoxide. In some embodiments, a base catalyst is an amine base.
  • Figure 1 is a flow diagram illustrating a process for preparing MPO according to an illustrative embodiment of the invention.
  • 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.
  • Macrocyclic polyester oligomers that may be employed 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( 1,3 -propylene terephthalate) (cPPT), macrocyclic poly(l,4-cyclohexylenedimethylene terephthalate) (cPCT), macrocyclic poly(ethylene terephthalate) (cPET), and macrocyclic poly(l,2-ethylene 2,6- naphthalenedicarboxylate) (cPEN) oligomers, and copolyester oligomers comprising two or more of the above monomer repeat units.
  • cPBT macrocyclic poly(l ,4- butylene terephthalate)
  • cPPT macrocyclic poly( 1,3 -propylene terephthalate)
  • cPCT macrocyclic poly(l,4-cyclohexylenedimethylene terephthalate)
  • cPET macrocyclic poly(ethylene tere
  • macrocyclic ester homo- and co-oligomers produced via methods of this invention include oligomers having a general structural repeat unit of the formula:
  • 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, respectively, appear below:
  • 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.
  • known methods for the conversion of TP A to DMT may be used.
  • 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
  • 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.
  • phenol di-ester refers to a terephthalate where both carboxyl groups are ester groups, and wherein each ester group comprises a carboxyl oxygen bonded to a phenyl group.
  • substantially homo- or co-polyester oligomer is understood to mean a polyester oligomer wherein the structural repeat units are substantially identical or substantially composed of two or more different structural repeat units, respectively.
  • the polyester oligomers described herein include substantially homo-polyester oligomers as well as substantially co- polyester oligomers.
  • terephthalate di-ester refers to a terephthalate where both carboxyl groups are ester groups.
  • the organic solvent is a high-purity hydrocarbon solvent, for example, such as Drakesol 165, manufactured by Orica Chemicals, which is composed of acid-treated light petroleum distillates. Other similar solvents may be used, as well.
  • the organic solvent may include at least one member selected from the group consisting of dibutyl ether, decane, dodecane, tetradecane, hexadecane, octadecane, heptane, toluene, xylene, trimethylbenzene, tetramethylbenzene,
  • ethylbenzene propylbenzene, naphthalene, methylnaphthalene, biphenyl, triphenyl, diphenyl ether (or a halogenated derivative thereof), anisol, pyridine, triethylamine, methylene chloride, dimethyoxybenzene, chlorobenzene, dichlorobenzene,
  • the organic solvent may include oDCB, toluene, o-xylene, pyridine, triethylamine, heptane, dibutyl ether, decane, dodecane, or trichlorobenzene (TCB).
  • the organic solvent may include toluene.
  • Base catalysts that may be used to practice the invention include known organic, inorganic bases, and combinations thereof.
  • the base catalyst is an organic base.
  • the catalyst is an amine.
  • the base catalyst is a tertiary amine.
  • a catalyst is a trialkylamine, dialkylamine or partially unsaturated or aromatic heterocyclic amine.
  • the base catalyst is triethylamine, DIPEA, N-methyl morpholine, DABCO, diisopropylamine, DBU, DMAP, PPTS, triazabicyclodecene (TBD), or imidazole.
  • the base catalyst is TBD.
  • a base catalyst is a metal alkoxides or carbonate.
  • a base catalyst is sodium bicarbonate, sodium carbonate, or potassium carbonate. In some embodiments, a base catalyst is a sodium or potassium alkoxide. In some embodiments, a base catalyst is sodium methoxide. In other embodiments, a base catalyst is potassium methoxide.
  • FIG. 1 is a schematic diagram of a process 100 for preparing MPO according to an illustrative embodiment. Certain embodiments involve methods and processes for performing the trans-esterification reaction of the reactor 104. Other embodiments involve methods and processes for performing an initial esterification reaction 102 to produce a product (e.g., a di-ester such as DPT) that is fed into the trans- esterification reactor 104. Other embodiments additionally involve performing a separation of MPO from a product stream, e.g., by running the product through a first heat exchanger 106, through a hot filter 108, through a second heat exchanger 110, and/or through a cold filter 112, after which the remaining MPO product is sent for purification, pelletization, and/or packaging.
  • a product stream e.g., a product stream, e.g., by running the product through a first heat exchanger 106, through a hot filter 108, through a second heat exchanger 110, and/or through a cold filter 112, after
  • terephthalic acid and phenol are fed into the esterification reactor 102, which takes place at a temperature from about 180 °C to about 300 °C.
  • the reaction produces H 2 0, which is released.
  • At least a portion of the phenol fed into the esterification reactor 102 may be the phenol that is produced in the trans-esterification reactor 104 and recycled into the esterification reactor 102.
  • the product of the esterification reactor 102 in this example is DPT.
  • the DPT produced in the esterification reactor 102 is fed into the trans- esterification reactor 104, along with butanediol, base catalyst, and solvent, examples of which are described herein.
  • the reaction mixture is maintained at a temperature from about 230 °C to about 260 °C in the trans-esterification reactor.
  • a base catalyst that is found to work particularly well is TBD.
  • the phenol is more easily replaced as an end group by the diol and has a favorable equilibrium with the desired diol. Use of phenol makes the reaction much faster than use of a methyl, ethyl, or butyl end group, for example.
  • the base catalyst does not react with the diol, so no THF or acetaldehyde is formed.
  • the reaction is run at low solids concentration (e.g., at a concentration no greater than about 5 wt.%, no greater than about 4 wt.%, no greater than about 3 wt.%, no greater than about 2 wt.%, or no greater than about 1 wt.%).
  • the evolved phenol is redirected back into the esterification reactor 102, while a product stream proceeds into the first heat exchanger 106.
  • Separation of MPO from the reaction mixture leaving the trans- esterification reactor is performed by reducing the temperature of the reaction mixture.
  • the reaction mixture is maintained within a temperature range in which the polyester linears that are produced substantially precipitate out of the reaction mixture (e.g., at least about 80 wt.% of the polyester linears in solution precipitate out), but in which the MPO substantially does not precipitate out of the reaction mixture (e.g., at least about 80 wt.% of the MPO in solution stays in solution).
  • a substantial portion of the base catalyst associates with (e.g., adsorbs to, binds to, or attaches to) the polyester linears, so a substantial portion of the base catalyst (e.g., at least about 95 wt.%, at least about 98 wt.%), at least about 99 wt.%, at least about 99.5 wt.%, or at least about 99.9 wt.%) can be removed from the reaction mixture by precipitation.
  • the recovered catalyst and/or recovered polyester linears may be recycled back into the trans- esterification reactor 104.
  • the first heat exchanger 106 takes the product reaction mixture from about 240 °C down to a temperature from about 120 °C to about 180 °C.
  • the product enters the hot filter 108, and the MPO-containing mixture proceeds to the second heat exchanger 110 while another portion is recycled to the first heat exchanger 106.
  • the second heat exchanger 1 10 takes the feed down to a lower temperature, for example, from a temperature from 120°C - 180°C to a temperature 40°C - 100°C, after which the product enters the cold filter 112.
  • a portion of the mixture containing MPO is removed from the cold filter 112 for purification, pelletization, and packaging, while another portion of the mixture is fed back into the second heat exchanger 110.
  • the integration % includes all byproducts and intermediates based on HPLC results

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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 des procédés et des systèmes pour préparer des oligomères de polyesters macrocycliques (MPO) par catalyse basique. On a trouvé que les catalyseurs basiques sont efficaces dans la production de MPO, et qu'ils réduisent le potentiel de sous-produits indésirables comme des furanes (par exemple, THF) et l'acétaldéhyde, qui résultent de réactions secondaires de diols.
PCT/US2014/026311 2013-03-13 2014-03-13 Procédés de préparation d'oligomère de polyester par catalyse basique WO2014160317A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201361780608P 2013-03-13 2013-03-13
US61/780,608 2013-03-13
US201461940399P 2014-02-15 2014-02-15
US61/940,399 2014-02-15

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