WO2011062600A1 - Polycondensation avec un réacteur malaxeur - Google Patents

Polycondensation avec un réacteur malaxeur Download PDF

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Publication number
WO2011062600A1
WO2011062600A1 PCT/US2009/067867 US2009067867W WO2011062600A1 WO 2011062600 A1 WO2011062600 A1 WO 2011062600A1 US 2009067867 W US2009067867 W US 2009067867W WO 2011062600 A1 WO2011062600 A1 WO 2011062600A1
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polymer
melt viscosity
reactor
acid
mole percent
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PCT/US2009/067867
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English (en)
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Joseph James Duffy
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E. I. Du Pont De Nemours And Company
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Publication of WO2011062600A1 publication Critical patent/WO2011062600A1/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
    • C08G63/88—Post-polymerisation treatment

Definitions

  • This invention relates to the use of a reactor, more specifically a wiped film evaporator or a kneader reactor, to boost the melt viscosity and/or molecular weight of polymers.
  • a reactor more specifically a wiped film evaporator or a kneader reactor.
  • these reactors are used to increase the viscosity of certain polyester polymers and copolymers after they are produced.
  • polyesters and copolymers of polyesters are useful in a wide variety of end-uses, including but not limited to fibers, films and other shaped articles.
  • these polyesters and copolyesters can also exhibit low melt viscosity and thus can exhibit non-optimal performance during processing to make these materials. Non-optimal performance due to low molecular weight may also occur during use. While other monomers or additives can be added to these polymers to increase their melt viscosity and/or molecular weight, these materials can negatively impact the final product properties.
  • the present invention provides polymers with increased the melt viscosity of homopolymers and copolymers.
  • the present invention relates to a polymer having a first melt viscosity of at least about 1000 poise and a second melt viscosity of at least about 1000 poise greater than said first melt viscosity, said second melt viscosity achieved after post polymerization processing of said polymer.
  • the present invention further relates to a process for increasing polymer viscosity, comprising:
  • the process of the present invention uses a reactor to increase the melt viscosity, including wiped film evaporators and kneader reactors.
  • the polymers described herein are generally condensation polymers, i.e., those formed when two reactive end-groups join and a small molecule is eliminated during synthesis. While many polymers are condensation polymers, ones of particular interest in the present invention are polyesters. Within the classification of polyesters, those of prime interest are poly(trimethylene terephthalate) homopolymers and
  • copolymers are also herein referred to copolyesters, and are of the general class of aliphatic-aromatic copolyesters. These aliphatic-aromatic copolyesters are further described below.
  • copolyesters are typically semicrystalline, and are prepared via the polymerization of linear aliphatic glycols with terephthalic acid, dimethyl terephthalate, linear aliphatic dicarboxylic acids, and branched dicarboxylic acids, glycols, and comonomers including hydroxy-carboxylic acids, alicyclic diol or dicarboxylic acids, and second aromatic diacids as comonomers.
  • glycol and diol
  • diol are used interchangeably to refer to general compositions of a primary, secondary, or tertiary alcohol containing two hydroxyl groups.
  • the term "semicrystalline" is intended to indicate that some fraction of the polymer chains of the aromatic-aliphatic copolyesters reside in a crystalline phase with the remaining fraction of the polymer chains residing in a non-ordered glassy amorphous phase.
  • the crystalline phase is characterized by a melting temperature, Tm, and the amorphous phase by a glass transition temperature, Tg, which can be 5 measured using Differential Scanning Calorimetry (DSC).
  • DSC Differential Scanning Calorimetry
  • ester, lactone, anhydride, or ester-forming derivatives of the various dicarboxylic acids and hydroxy-carboxylic acids may be used in the polymerizations in lieu of the diacids and hydroxy-carboxylic acids themselves.
  • carboxylic acids is intended to include all aliphatic, alicyclic, or aromatic dicarboxylic acids, aliphatic diols, or aliphatic hydroxy-carboxylic acids that are substituted with aliphatic, alicyclic, or aromatic side-chain groups containing at least 2 carbon atoms and optionally containing oxygen atoms.
  • the aliphatic side-chain itself may be a linear or branched aliphatic i s group, and the alicyclic and aromatic side-chains may be additionally
  • the optional oxygen atoms can be in the form of ethers or polyethers.
  • the side-chain groups are not intended to include long-chain branches that are generated during the course of polymerization by tri- and polyfunctional comonomers
  • ionic substituents such as anionic sulfonate and phosphate groups.
  • the dicarboxylic acid component consists essentially of between about 100 and 40 mole percent of a terephthalic acid component, 5 between about 0 and 60 mole percent of an linear aliphatic dicarboxylic acid component, and between about 0 and 60 mole percent of a branched dicarboxylic acid component all of which are based on 100 mole percent of total dicarboxylic acid component.
  • the glycol component consists essentially of between about 100 to 60 mole percent of a linear 0 glycol component, between about 0 to 4 mole percent of a dialkylene
  • the glycol component and between about 0 and 40 mole percent of a branched glycol component all of which are based on 100 mole percent total glycol component.
  • the branched hydroxy-carboxylic acid component is optional and consists essentially of between about 0 and 150 mole percent of a branched hydroxy-carboxylic acid component based on the total dicarboxylic acid component.
  • the sum of the mole percents for the branched dicarboxylic acid component, the branched glycol component, and the branched hydroxy-carboxylic acid component as defined above must be at least about 2 mole percent.
  • Terephthalic acid components that are useful in the aliphatic- aromatic copolyesters include terephthalic acid, bis(glycolates) of terephthalic acid, and lower alkyl esters of terephthalic acid having from 8 to 20 carbon atoms.
  • Specific examples of desirable terephthalic acid components include terephthalic acid, dimethyl terephthalate, bis(2- hydroxyethyl)terephthalate, bis(3-hydroxypropyl) terephthalate, bis(4- hydroxybutyl)terephthalate.
  • Linear aliphatic dicarboxylic acid components that are useful in the aliphatic-aromatic copolyesters include unsubstituted and methyl- substituted aliphatic dicarboxylic acids and their lower alkyl esters having from 2 to 36 carbon atoms.
  • linear aliphatic dicarboxylic acid components include, oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl succinate, glutaric acid, dimethyl glutarate, 3,3-dimethylglutaric acid, adipic acid, dimethyl adipate, pimelic acid, suberic acid, azelaic acid, dimethyl azelate, sebacic acid, dimethyl sebacate, undecanedioic acid,1 ,10-decanedicarboxylic acid, 1 ,1 1 -undecanedicarboxylic acid (brassylic acid), 1 ,12- dodecanedicarboxylic acid, hexadecanedioic acid, docosanedioic acid, tetracosanedioic acid, and mixtures derived therefrom.
  • the linear aliphatic dicarboxylic acid component is derived from a renewable biological source, in particular azelaic acid, sebacic acid, and brassylic acid.
  • a renewable biological source in particular azelaic acid, sebacic acid, and brassylic acid.
  • essentially any linear aliphatic dicarboxylic acid or derivative known can be used, including mixtures thereof.
  • Branched dicarboxylic acid components that are useful in the aliphatic-aromatic copolyesters include branched aliphatic, alicyclic, and aromatic dicarboxylic acids and their bis(glycolates) and lower alkyl esters having from 8 to 48 carbon atoms.
  • desirable branched aliphatic dicarboxylic acid components include branched derivatives of the linear aliphatic dicarboxylic acids and dimers of unsaturated aliphatic carboxylic acids derived from renewable biological sources.
  • Examples of desirable branched alicyclic dicarboxylic acid components include substituted derivatives of 1 ,4-cyclohexanedicarboxylates, 1 ,3- cyclohexanedicarboxylat.es, and 1 ,2-cyclohexanedicarboxylates.
  • Examples of desirable branched aromatic dicarboxylic acid components include substituted derivatives of terephthalates, isophthalates, phthalates, naphthalates and bibenzoates.
  • components include 3-hexylglutaric acid, 3-phenylglutaric acid, 3,3- tetramethyleneglutaric acid, 3,3-tetramethyleneglutaric anhydride, 3- methyl-3-ethylglutaric acid, 3-tert-butyladipic acid, 3-hexyladipic acid, 3- octyladipic acid, 3-(2,4,4-trimethylpentyl)-hexanedioic acid, diethyl dibutylmalonate, 1 ,1 -cyclohexanediacetic acid, cyclohexylsuccinic acid, 5- tert-butylisophthalic acid, 5-hexyloxyisophthalic acid, 5- octadecyloxyisophthalic acid, 5-phenoxyisophthalic acid, 2- phenoxyterephthalic acid, 2,5-biphenyldicarboxylic acid, 3,5- biphenyldicarboxylic acid, 5-tert-
  • hydrogenated fatty acid dimers essentially any branched dicarboxylic acid or derivative known can be used, or as a mixture of two or more thereof.
  • Linear glycol components that typically find use in the embodiments disclosed herein include unsubstituted and methyl-substituted alkanediols with 2 to 10 carbon atoms. Examples include 1 ,2-ethanediol, 1 ,2- propanediol, 1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol, and 1 ,4- butanediol.
  • the linear glycol components are derived from a renewable biological source, in particular 1 ,3-propanediol and 1 ,4- butanediol.
  • Dialkylene glycol components that are found in the embodiments disclosed herein can be added to the polymerizations as monomers, but typically are generated in situ by dimerization of the linear glycol components under the conditions required for polymerization.
  • Methods to control the dimerization of the linear glycols include monomer selection such as choice between dicarboxylic acids and their derivatives or inclusion of sulfonated monomers, catalyst selection, catalyst amount, inclusion of strong protonic acids, addition of basic compounds such as tetramethylammonium hydroxide or sodium acetate, and other process conditions such as temperatures and residence times.
  • the dialkylene glycol component is present from about 0 to 4 mole based on 100 mole percent total glycol component.
  • the dialkylene glycol component is present in at least about 0.1 mole percent based on 100 mole percent total glycol component.
  • Branched glycol components that are typically found in the embodiments disclosed herein include branched derivatives of linear aliphatic diols and dimer diols derived from unsaturated aliphatic carboxylic acids derived from renewable biological sources. Examples include 1 ,2-butanediol, 1 ,2-hexanediol, 1 ,2-octanediol, 1 ,2-decanediol, 1 ,2-dodecanediol, 2-butyl-2-ethyl-1 ,3-propanediol, and hydrogenated fatty acid dimer diol. However, essentially any branched diol known can be used, or as a mixture of two or more thereof.
  • Branched hydroxy-carboxylic acid components that typically find use in the embodiments disclosed herein include branch- and hydroxy- substituted aliphatic carboxylic acids and their lactones, lactides, bis(glycolates), and lower alkyl esters having a total of from 4 to 30 carbon atoms.
  • the branched hydroxy-carboxylic acid components are derived from a renewable biological source, in particular 12-hydroxystearic acid.
  • Aromatic dicarboxylic acid components useful in the aliphatic- aromatic copolyesters include unsubstituted and methyl-substituted aromatic dicarboxylic acids, bis(glycolates) of aromatic dicarboxylic acids, and lower alkyl esters of aromatic dicarboxylic acids having from 8 carbons to 20 carbons.
  • desirable dicarboxylic acid components include those derived from phthalates, isophthalates, naphthalates and bibenzoates.
  • aromatic dicarboxylic acid component examples include phthalic acid, dimethyl phthalate, phthalic anhydride, bis(2-hydroxyethyl)phthalate, bis(3- hydroxypropyl)phthalate, bis(4-hydroxybutyl)phthalate, isophthalic acid, dimethyl isophthalate, bis(2-hydroxyethyl)isophthalate, bis(3- hydroxypropyl)isophthalate, bis(4-hydroxybutyl)isophthalate, 2,6- naphthalene dicarboxylic acid, dimethyl-2,6-naphthalate, 2,7- naphthalenedicarboxylic acid, dimethyl-2,7-naphthalate, 1 ,8-naphthalene dicarboxylic acid, dimethyl 1 ,8-naphthalenedicarboxylate, 1 ,8-naphthalic anhydride, 3,4'-diphenyl ether dicarboxylic acid, dimethyl-3,4'-diphenyl ether dicarbox
  • the second aromatic dicarboxylic acid component is derived from phthalic anhydride, phthalic acid, isophthalic acid, or mixtures thereof.
  • any aromatic dicarboxylic acid or derivative known in the art can be used for the second aromatic diacid, including mixtures thereof.
  • the monomers of this invention are not intended to include ionic substituents, such as anionic sulfonate and phosphate groups.
  • the term alicyclic diol is intended to include all non-linear aliphatic diols containing rings of carbon atoms linked by single bonds.
  • alicyclic dicarboxylic acid is intended to include all non-linear aliphatic dicarboxylic acids containing rings of carbon atoms linked by single bonds.
  • Alicyclic dicarboxylic acids that are useful in the aliphatic-aromatic copolyesters include alicyclic dicarboxylic acids and their lower alkyl esters having 5 to 36 carbon atoms. Specific examples include 1 ,4-cyclohexane dicarboxylic acid, 1 ,2-cyclohexane dicarboxylic acid, 1 ,3-cyclopentane dicarboxylic acid and ( ⁇ )-1 ,8,8-Trimethyl-3-oxabicyclo[3.2.1 ]octane-2,4- dione However, essentially any alicyclic dicarboxylic acid or derivative having 5 to 36 carbon atoms can be used, including mixtures thereof.
  • the dicarboxylic acid component consists essentially of about 70 to 50 mole percent of the terephthalic acid component, about 20 to 50 mole percent of the linear aliphatic dicarboxylic acid component, and about 0 to 30 mole percent of the branched dicarboxylic acid component.
  • the glycol component consists essentially of about 100 to 70 mole percent of the linear glycol component, about 0 to 4 mole percent of the dialkylene glycol component, and about 0 to 30 mole percent of the branched glycol component.
  • the branched hydroxy-carboxylic acid component is still optional at 0 to 30 mole percent based on the total dicarboxylic acid component, and either the branched dicarboxylic acid component, the branched glycol component, or the branched hydroxy-carboxylic acid component is solely present in at least about 6 mole percent.
  • the optional branched hydroxy-carboxylic acid component is omitted from the composition.
  • the dicarboxylic acid component consists essentially of about 60 to 52 mole percent of the terephthalic acid component, about 32 to 40 mole percent of the linear aliphatic dicarboxylic acid component, and about 0 to 16 mole percent of the branched dicarboxylic acid component.
  • the glycol component consists essentially of about 100 to 84 mole percent of the linear glycol component, about 0 to 4 mole percent of the dialkylene glycol component, and about 0 to 16 mole percent of the branched glycol component. Either the branched dicarboxylic acid component or the branched glycol component is solely present in at least about 6 mole percent.
  • the branched dicarboxylic acid component and the branched glycol component are omitted from the composition.
  • the dicarboxylic acid component consists essentially of about 100 to 70 mole percent of the terephthalic acid component and about 0 to 30 mole percent of the linear aliphatic dicarboxylic acid component.
  • the glycol component consists essentially of about 100 to 96 mole percent of the linear glycol component and about 0 to 4 mole percent of the dialkylene glycol component.
  • the branched hydroxy-carboxylic acid component is not optional and is present in about 30 to 150 mole percent.
  • the dicarboxylic acid component consists essentially of about 70 to 50 mole percent of the terephthalic acid component, about 20 to 50 mole percent of the linear aliphatic dicarboxylic acid component, and about 0 to 30 mole percent of the alicyclic dicarboxylic acid component.
  • the glycol component consists essentially of about 100 to 70 mole percent of the linear glycol component, about 0 to 4 mole percent of the dialkylene glycol component, and about 0 to 30 mole percent of the alicyclic glycol component. Either the alicyclic dicarboxylic acid component or the alicyclic glycol component is solely present in at least about 6 mole percent.
  • the dicarboxylic acid component consists essentially of about 60 to 55 mole percent of the terephthalic acid component, about 30 to 40 mole percent of the linear aliphatic dicarboxylic acid component, and about 0 to 20 mole percent of the alicyclic dicarboxylic acid component.
  • the glycol component consists essentially of about 100 to 85 mole percent of the linear glycol component, about 0 to 4 mole percent of the dialkylene glycol component, and about 0 to 15 mole percent of the alicyclic glycol component. Either the alicyclic dicarboxylic acid component or the alicyclic glycol component is solely present in at least about 6 mole percent.
  • the acid component will comprise between about 80 and 40 mole percent of a terephthalic acid component based on 100 mole percent total acid component, between about 10 and 60 mole percent of a linear aliphatic dicarboxylic acid component based on 100 mole percent of total acid component, and between about 2 and 30 mole percent of a second aromatic dicarboxylic acid component based on 100 mole percent of total acid component.
  • the glycol component consists essentially of about 100 to 96 mole percent of a linear glycol component based on 100 mole percent total glycol component, and about 0 to 4 mole percent of a dialkylene glycol component based on 100 mole percent total glycol component.
  • the acid component will comprise between about 69 and
  • the acid component will comprise between about 59 and 51 mole percent of a terephthalic acid component based on 100 mole percent total acid component, between about 34 and 44 mole percent of a linear aliphatic dicarboxylic acid component based on 100 mole percent of total acid component, and between about 6 and 14 mole percent of a second aromatic dicarboxylic acid component based on 100 mole percent of total acid component.
  • the ratio of the mole percent of the second aromatic dicarboxylic acid to terephthalic acid is less than about 3:4. More typically, the ratio of the mole percent of the second aromatic dicarboxylic acid to terephthalic acid is less than about 19:46. Often, the ratio of the mole percent of the second aromatic dicarboxylic acid to terephthalic acid is less than about 14:51 . In some embodiments, the ratio of the mole percent of the second aromatic dicarboxylic acid to terephthalic acid is less than about 19:81 .
  • the ratio of the mole percent of the second aromatic 5 dicarboxylic acid to terephthalic acid is greater than about 1 :20. More typically, the ratio of the mole percent of the second aromatic dicarboxylic acid to terephthalic acid is greater than about 2:23. Often, the ratio of the mole percent of the second aromatic dicarboxylic acid to terephthalic acid is greater than about 6:51 . In some embodiments, the ratio of the mole 10 percent of the second aromatic dicarboxylic acid is greater than about 5:26.
  • the ratio of the combined mole percents of all aromatic dicarboxylic acids to all linear aliphatic dicarboxylic acids is greater than 2:3. More typically, the ratio of the combined mole percents of all aromatic i s dicarboxylic acids to all linear aliphatic dicarboxylic acids is greater than 51 :49. Often, the ratio of the combined mole percents of all aromatic dicarboxylic acids to all linear aliphatic dicarboxylic acids is greater than 56:44. In some embodiments, the ratio of the combined mole percents of all aromatic dicarboxylic acids to all linear aliphatic dicarboxylic acids is 0 greater than 61 :39.
  • the 1 ,3-propanediol used in the embodiments disclosed herein is preferably obtained biochemically from a renewable source ("biologically- derived" 1 ,3-propanediol).
  • a particularly preferred source of 1 ,3- propanediol is via a fermentation process using a renewable biological 5 source.
  • biochemical routes to 1 ,3-propanediol (PDO) have been described that utilize feedstocks produced from biological and renewable resources such as corn feed stock.
  • bacterial strains able to convert glycerol into 1 ,3-propanediol are found in the species Klebsiella,
  • US5633362 US5686276 and US5821092 discloses, inter alia, a process for the biological production of 1 ,3-propanediol from glycerol using recombinant organisms.
  • the process incorporates E. coli bacteria, transformed with a heterologous pdu diol dehydratase gene, having specificity for 1 ,2-propanediol.
  • the transformed E. coli is grown in the presence of glycerol as a carbon source and 1 ,3- propanediol is isolated from the growth media. Since both bacteria and yeasts can convert glucose (e.g., corn sugar) or other carbohydrates to glycerol, the processes disclosed in these publications provide a rapid, inexpensive and environmentally responsible source of 1 ,3-propanediol monomer.
  • the biologically-derived 1 ,3-propanediol such as produced by the processes described and referenced above, contains carbon from the atmospheric carbon dioxide incorporated by plants, which compose the feedstock for the production of the 1 ,3-propanediol.
  • the biologically-derived 1 ,3-propanediol preferred for use in the context of the present invention contains only renewable carbon, and not fossil fuel- based or petroleum-based carbon.
  • compositions of the present invention can be characterized as more natural and having less environmental impact than similar compositions comprising petroleum based diols.
  • the biologically-derived 1 ,3-propanediol, and polytrimethylene terephthalate based thereon, may be distinguished from similar
  • 14 C can be measured by accelerator mass spectrometry (AMS), with results given in units of "fraction of modern carbon" (f M ).
  • AMS accelerator mass spectrometry
  • f M fraction of modern carbon
  • ⁇ M is defined by National Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs) 4990B and 4990C, known as oxalic acids standards HOxl and HOxll, respectively.
  • SRMs Standard Reference Materials
  • the fundamental definition relates to 0.95 times the 14 C/ 12 C isotope ratio HOxl (referenced to AD 1950). This is roughly equivalent to decay-corrected pre-lndustrial Revolution wood.
  • ⁇ M s 1 .1 The stable carbon isotope ratio ( 13 C/ 12 C) provides a complementary route to source discrimination and apportionment.
  • the 13 C/ 12 C ratio in a given biosourced material is a consequence of the 13 C/ 12 C ratio in atmospheric carbon dioxide at the time the carbon dioxide is fixed and also reflects the precise metabolic pathway. Regional variations also occur. Petroleum, C 3 plants (the broadleaf), C 4 plants (the grasses), and marine carbonates all show significant differences in 13 C/ 12 C and the
  • 13 C shows large variations due to isotopic fractionation effects, the most significant of which for the instant invention is the photosynthetic mechanism.
  • the major cause of differences in the carbon isotope ratio in plants is closely associated with differences in the pathway of photosynthetic carbon metabolism in the plants, particularly the reaction occurring during the primary carboxylation, i.e., the initial fixation of atmospheric CO2.
  • Two large classes of vegetation are those that incorporate the "C 3 " (or Calvin-Benson) photosynthetic cycle and those that incorporate the "C 4 " (or Hatch-Slack) photosynthetic cycle.
  • C3 plants, such as hardwoods and conifers, are dominant in the temperate climate zones.
  • the primary CO2 fixation or carboxylation reaction involves the enzyme ribulose-1 ,5- diphosphate carboxylase and the first stable product is a 3-carbon compound.
  • C 4 plants include such plants as tropical grasses, corn and sugar cane.
  • an additional carboxylation reaction involving another enzyme, phosphenol-pyruvate carboxylase is the primary carboxylation reaction.
  • the first stable carbon compound is a 4-carbon acid, which is subsequently decarboxylated. The CO2 thus released is refixed by the C3 cycle.
  • Both C 4 and C3 plants exhibit a range of 13 C/ 12 C isotopic ratios, but typical values are ca.
  • Notations for the per mil deviations from PDB is 5 13 C. Measurements are made on CO2 by high precision stable ratio mass spectrometry (IRMS) on molecular ions of masses 44, 45 and 46.
  • IRMS high precision stable ratio mass spectrometry
  • Biologically-derived 1 ,3-propanediol, and compositions comprising biologically-derived 1 ,3-propanediol therefore, may be completely distinguished from their petrochemical derived counterparts on the basis of 14 C (fivi) and dual carbon-isotopic fingerprinting, indicating new
  • compositions of matter comprising both “new” and “old” carbon isotope profiles.
  • the instant materials may be followed in commerce on the basis of their unique profile and for the purposes of defining competition, for determining shelf life, and especially for assessing environmental impact.
  • the 1 ,3-propanediol used as a reactant or as a
  • the component of the reactant in making the polymers disclosed herein will have a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis.
  • Particularly preferred are the purified 1 ,3-propanediols as disclosed in US7038092, US7098368, US708431 1 and US20050069997A1 all of which are incorporated by reference.
  • the purified 1 ,3-propanediol preferably has the following
  • composition having a CIELAB "b * " color value of less than about 0.15 ASTM D6290
  • absorbance at 270 nm of less than about 0.075 ASTM D6290
  • a peroxide composition of less than about 10 ppm; and/or (4) a concentration of total organic impurities (organic compounds other than 1 ,3-propanediol) of less than about 400 ppm, more preferably less than about 300 ppm, and still more preferably less than about 150 ppm, as measured by gas chromatography.
  • the aliphatic-aromatic copolyesters can be polymerized from the disclosed monomers by any process known for the preparation of polyesters. Such processes can be operated in either a batch, semi- batch, or in a continuous mode using suitable reactor configurations.
  • the specific batch reactor process used to prepare the polymers disclosed in the embodiments herein is equipped with a means for heating the reaction to 260°C, a fractionation column for distilling off volatile liquids, an efficient stirrer capable of stirring a high viscosity melt, a means for blanketing the reactor contents with nitrogen, and a vacuum system capable of achieving a vacuum of less than 1 mm of Hg.
  • reactor configuration settings are generally set depending on the polymers being processed.
  • This batch process was generally carried out in two steps.
  • diacid monomers or their derivatives were reacted with a diol in the presence of an ester interchange catalyst. This resulted in the formation of alcohol and/or water, which distilled out of the reaction vessel, and diol adducts of the diacids.
  • the exact amount of monomers charged to the reactor was readily determined by a skilled practitioner depending on the amount of polymer desired and its composition. It was advantageous to use excess diol in the ester interchange step, with the excess distilled off during the second, polycondensation step. A diol excess of 10 to 100% was commonly used.
  • Catalysts are generally known in the art, and preferred catalysts for this process were titanium alkoxides.
  • the amount of catalyst used was usually 20 to 200 parts titanium per million parts polymer.
  • the combined monomers are heated gradually with mixing to a temperature in the range of 200 to 250°C.
  • the reactor may be heated directly to 250°C, or there may be a hold at a temperature in the range of 200 to 230°C to allow the ester interchange to occur and the volatile products to distill out without loss of the excess diol.
  • the ester interchange step was usually completed at a temperature ranging from 240 to 260°C. The completion of the interchange step was determined from the amount of alcohol and/or water collected and by falling temperatures at the top of the distillation column.
  • the second step, polycondensation, was carried out at 240 to 260°C under vacuum to distill out the excess diol. It was preferred to apply the vacuum gradually to avoid bumping of the reactor contents. Stirring was continued under full vacuum (less than 1 mm Hg) until the desired melt viscosity was reached. A practitioner experienced with the reactor would be able to determine if the polymer had reached the desired melt viscosity from the torque on the stirrer motor.
  • the aliphatic-aromatic copolyesters have sufficiently high molecular weights to provide suitable melt viscosity for processing into shaped articles, and useful levels of mechanical properties in said articles.
  • weight average molecular weights Mw from about 20,000 g/mol to about 150,000 g/mol are useful. More typical are Mw from about 50,000 g/mol to about 130,000 g/mol. Most typical are Mw from about 80,000 g/mol to about 1 10,000 g/mol.
  • molecular weights are often correlated to solution viscosities, such as intrinsic or inherent viscosity.
  • the molecular weights above generally correspond to intrinsic viscosity (IV) values from about 0.5 dL/g to about 2.0 dL/g. More typical are IV values from about 1 .0 dL/g to about 1 .8 dL/g. Most typical are IV values from about 1 .3 dL/g to about 1 .6 dL/g.
  • IV intrinsic viscosity
  • Suitable chain extenders include diisocyanates, polyisocyanates, dianhydrides, diepoxides, polyepoxides, bis-oxazolines, carbodiimides, and divinyl ethers, which can be added at the end of the polycondensation step, during processing on mechanical extrusion equipment, or during
  • copolyesters into desired shaped articles.
  • desirable chain extenders include hexamethylene
  • chain extenders are typically used at 0.1 to 2 weight percent with respect to the copolyesters.
  • the aliphatic-aromatic copolyesters can be blended with other polymeric materials.
  • Such polymeric materials can be biodegradable or not biodegradable, and can be naturally derived, modified naturally derived or synthetic.
  • biodegradable polymeric materials suitable for blending with the aliphatic-aromatic copolyesters include
  • copolyetheresters aliphatic-aromatic copolyamideesters, sulfonated aliphatic-aromatic copolyesters, sulfonated aliphatic-aromatic
  • copolyetheresters sulfonated aliphatic-aromatic copolyamideesters, and copolymers and mixtures derived therefrom.
  • blendable biodegradable materials include the Biomax® sulfonated aliphatic-aromatic copolyesters of the DuPont Company, the Eastar Bio® aliphatic-aromatic copolyesters of the Eastman Chemical Company, the Ecoflex® aliphatic-aromatic copolyesters of the BASF corporation, poly(1 ,4-butylene terephthalate-co-adipate, (50:50, molar), the EnPo® polyesters of the Ire Chennical Connpany, poly(1 ,4-butylene succinate), the Bionolle® polyesters of the Showa High Polymer Company, poly(ethylene succinate), poly(1 ,4-butylene adipate-co-succinate) , poly(1 ,4-butylene adipate),
  • any biodegradable material can be blended with the aliphatic-aromatic copolyesters.
  • nonbiodegradable polymeric materials suitable for blending with the aliphatic-aromatic copolyesters include polyethylene, high density polyethylene, low density polyethylene, linear low density polyethylene, ultralow density polyethylene, polyolefins, ply(ethylene-co- glycidylmethacrylate), poly(ethylene-co-methyl (meth) acrylate-co-glycidyl acrylate), poly(ethylene-co-n-butyl acrylate-co-glycidyl acrylate), poly(ethylene-co-methyl acrylate), poly(ethylene-co-ethyl acrylate), poly(ethylene-co-butyl acrylate), poly(ethylene-co-(meth) acrylic acid), metal salts of poly(ethylene-co-(meth)acrylic acid), poly((meth)acrylates), such as poly(methyl methacrylate), poly(ethyl methacrylate),
  • Examples of natural polymeric materials suitable for blending with the aliphatic-aromatic copolyesters include starch, starch derivatives, modified starch, thermoplastic starch, cation ic starch, anionic starch, starch esters, such as starch acetate, starch hydroxyethyl ether, alkyl starches, dextrins, amine starches, phosphate starches, dialdehyde starches, cellulose, cellulose derivatives, modified cellulose, cellulose esters, such as cellulose acetate, cellulose diacetate, cellulose
  • priopionate cellulose butyrate, cellulose valerate, cellulose triacetate, cellulose tripropionate, cellulose tributyrate, and cellulose mixed esters, such as cellulose acetate propionate and cellulose acetate butyrate, cellulose ethers, such as methylhydroxyethylcellulose,
  • hydroxymethylethylcellulose carboxymethylcellulose, methyl cellulose, ethylcellulose, hydroxyethycellulose, and hydroxyethylpropylcellulose, polysaccharides, alginic acid, alginates, phycocolloids, agar, gum arabic, guar gum, acaia gum, carrageenan gum, furcellaran gum, ghatti gum, psyllium gum, quince gum, tamarind gum, locust bean gum, gum karaya, xantahn gum, gum tragacanth, proteins, prolamine, collagen and derivatives thereof such as gelatin and glue, casein, sunflower protein, egg protein, soybean protein, vegetable gelatins, gluten, and mixtures derived therefrom.
  • Thermoplastic starch can be produced, for example, as disclosed within U. S. Pat. No. 5,362,777. Essentially any natural polymeric material known can be blended with the aliphatic-aromatic copolyesters.
  • the molecular weights of the aliphatic-aromatic copolyesters can also be increased by post-polymerization processes, such as solid-phase polymerization and vacuum extrusion, both of which allow the efficient removal of any volatiles generated by polycondensation at their respective scales of temperature and time.
  • post-polymerization processes such as solid-phase polymerization and vacuum extrusion, both of which allow the efficient removal of any volatiles generated by polycondensation at their respective scales of temperature and time.
  • the benefit of these processes is that the composition of the copolyesters remains unperturbed by the processing conditions.
  • solid-phase polymerization a polyester or copolyester is held at a temperature below its melting point, more typically below the temperature at which the polymer particles begin to stick, and subjected to vacuum or a flow of dry atmosphere. This process is most beneficial for polyesters, such as polyethylene terephthalate, polytrimethylene
  • terephthalate and polybutylene terephthalate, which contain little or no comonomers that substantially reduce their melting points, typically greater than 200 °C.
  • a polyester or copolyester is 5 fed to a mechanical extruder at a suitable temperature to melt them and then subjected to high vacuum. This process is most beneficial for copolyesters, including all of the compositions whose preparation is described herein, due to their lower melting points, typically less than 200 °C. In each process, the temperature and time that is needed to obtain
  • the necessary increase in molecular weight due to polycondensation can be determined by taking samples or by monitoring the process outputs, such as the torque reading for the mechanical extruder.
  • reactors useful in the present invention include wiped film evaporators and mechanical extruders/kneader reactors. Suitable i s mechanical extruders/kneader reactors on which to process the
  • copolyesters are well known in the art and can be purchased from commercial vendors.
  • extruders and kneader reactors can be advantageously employed in vacuum extrusion, including single shaft, twin shaft, corotatory, or contrarotatory units.
  • Twin-screw extruders are 0 available from Coperion Werner & Pfleiderer (Stuttgart, Germany), and continuous kneader reactors from BUSS AG (LR series, Pratteln,
  • Wiped film evaporators can also be used in some embodiments, and are available from Pfaudler Reactor Systems (Rochester, NY) and LCI Corp. (Charlotte, NC).
  • the polymers described herein generally have first melt viscosities of around 1000 poise at 260 degrees C and 1/sec shear rate after their initial synthesis, and can be in any convenient form including
  • the polymer is then supplied to the reactor in any convenient way, including but not limited to a hopper, an extruder or the like. If the polymer is supplied in a solid form, the reactor can be configured to melt the polymer so that it can be processed in flowable form.
  • the polymer is processed through the reactor until the desired second melt viscosity is achieved.
  • This second melt viscosity is generally high enough to allow the processed polymer to be differentiated from the initial polymer product, and thus to give the desired mechanical properties suitable for the chosen end-use.
  • the second melt viscosity, achieved after processing could be anywhere from 2000 poise up to 12000 poise, or any viscosity that provides the desired mechanical properties. More particularly, the first melt viscosity can range from 1000 to 7000 poise, and the second melt viscosity could range from 2000 to 12000 poise at 260 degrees C, and at shear rates of about 1/second.
  • the residence time for the polymer in the reactor can be chosen based on many parameters, including but not limited to the type of polymer, the size of the reactor, the equipment speed, and the configuration of the reactor. This time can be determined by those skilled in the art. Generally, this process is
  • the polymer can be recycled through the reactor if the achieved melt viscosity is not high enough for the proposed end use. This can be done in batch, semi-batch or continuous mode.
  • the reactors described herein can be operated at a variety of different temperatures, pressures, etc., depending on the polymers and copolymers that are to be processed. For some materials, it may be advantageous to operate above the melting temperature for semi- crystalline polymers, and above the glass transition temperature of amorphous polymers, or even below these values for other polymers in the same classifications.
  • reactor parameters can be chosen so that the polymer can be fed into the reactor when it is already at a relatively high molecular weight (e.g., 7000 poise).
  • the melt viscosity of the polymer can be measured by any one of the following parameters
  • the aliphatic-aromatic copolyesters and blends formed therefrom can be used to make a wide variety of shaped articles.
  • Shaped articles i s that can be made from the aliphatic-aromatic copolyesters include films, sheets, fibers, filaments, bags, melt blown containers, molded parts such as cutlery, coatings, polymeric melt extrusion coatings on substrates, polymeric solution coatings onto substrates, laminates, and bicomponent, multi-layer, and foamed varieties of such shaped articles.
  • the aliphatic- 0 aromatic copolyesters are useful in making any shaped article that can be made from a polymer.
  • the aliphatic-aromatic copolyesters can be formed into such shaped articles using any known process therefore, including thermoplastic processes such as compression molding, thermoforming, extrusion, coextrusion, injection molding, blow molding, melt spinning, film 5 casting, film blowing, lamination, foaming using gases or chemical foaming agents, or any suitable combination thereof to prepare the desired shaped article.
  • thermoplastic processes such as compression molding, thermoforming, extrusion, coextrusion, injection molding, blow molding, melt spinning, film 5 casting, film blowing, lamination, foaming using gases or chemical foaming agents, or any suitable combination thereof to prepare the desired shaped article.
  • the aliphatic-aromatic copolyesters, their blends, and the shaped articles formed therefrom can include any known additive used in
  • the additives are preferably nontoxic, biodegradable, and derived from renewable biological sources.
  • Such additives include compatibilizers for the polymer blend components, antioxidants, thermal and UV stabilizers, flame retardants, plasticizers, flow enhancers, slip agents, rheology modifiers, lubricants, tougheners, pigments, antiblocking agents, inorganic and organic fillers, such as silica, clay, talc, chalk, titanium dioxide, carbon black, wood flour, keratin, chitin, refined feathers and reinforcing fibers, such as glass fibers and natural fibers like paper, jute and hemp.
  • a kneader reactor is preheated to 265 deg C and evacuated to 5 mm Hg pressure. Approximately one kilogram of polymer with relatively low molecular weight/low viscosity, and with a reduced amount or no catalyst, is melted, having a temperature of about 260 deg C, and fed by an extruder into the reactor. The reactor has a total volume of 3 liters or a working volume of 2 liters. The reactor's agitator is started, rotating initially at approximately 20 rpm, and then slowed to 3 rpm or less as the melt viscosity of the polymer builds toward as much as 7000 poise at 260 degrees C and 1 /second shear rate.
  • the agitator speed is adjusted to optimize or maximize the surface exposed to the vapor space, while minimizing the total volume of contents in the reactor.
  • the reactor is heated by a heating jacket or other means, and adjusted to maintain the melt temperature of the polymer to approximately 260 deg C.
  • the progress of the polycondensation reaction is monitored via agitator torque, recirculation or sampling of a sidestream through a viscometer.
  • the reactor pressure is lowered to encourage and increase the reaction rate. The pressure would typically be lowered to approximately 1 mm Hg.
  • the pressure of the reactor starts and remains at
  • the reactor can be pressurized to several psig to encourage flow of the viscous material into the pump inlet.
  • Molten polymer is then pumped through a die into a water bath and then into a strand cutter.
  • Molten polymer can also be alternatively pumped through a die as part of an underwater melt cutter.
  • the agitator typically continues to rotate slowly during at least the initial discharge of the reactor. After discharge of the contents that can be readily discharged, the reactor is again charged with relatively low molecular weight polymer.
  • the batch or batch-wise-continuous process then continues. Alternatively, this process is run in a continuous manner with a suitable reactor operating in plug flow or nearly plug flow conditions.

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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

La présente invention concerne l'utilisation d'un réacteur, plus spécifiquement un évaporateur à film tombant ou un réacteur malaxeur, afin d'augmenter la viscosité de polymères. L'utilisation de ces réacteurs pour augmenter la viscosité de certains polymères et copolymères de polyester après qu'ils aient été produits revêt un intérêt tout particulier.
PCT/US2009/067867 2009-11-19 2009-12-14 Polycondensation avec un réacteur malaxeur WO2011062600A1 (fr)

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US61/262,696 2009-11-19

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DE102011089056A1 (de) 2011-12-19 2013-06-20 Evonik Industries Ag Verfahren zur Herstellung von Polyestern
WO2015173310A1 (fr) * 2014-05-16 2015-11-19 Basf Se Production de polyamides par polymérisation hydrolytique suivie d'un traitement dans un malaxeur
KR20180018985A (ko) 2016-08-11 2018-02-22 주식회사 미래에스아이 스티렌-부타디엔 고무 용액과 표면 처리된 실리카의 혼합물로부터 습윤 마스터 배치의 제조방법
CN110195263A (zh) * 2019-06-20 2019-09-03 王维列 一种溶剂法生产再生纤维素纤维纺丝胶液的制备方法
US20210089920A1 (en) * 2019-09-20 2021-03-25 Axalta Coating Systems Ip Co., Llc Systems and methods for approximating a 5-angle color difference model
US11535705B2 (en) * 2018-01-24 2022-12-27 Sk Chemicals Co., Ltd. Polycarbonate ester and preparation method therefor

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Publication number Priority date Publication date Assignee Title
DE102011089056A1 (de) 2011-12-19 2013-06-20 Evonik Industries Ag Verfahren zur Herstellung von Polyestern
WO2013092273A1 (fr) 2011-12-19 2013-06-27 Evonik Industries Ag Procédé de production de polyester
CN103987756A (zh) * 2011-12-19 2014-08-13 赢创工业集团股份有限公司 生产聚酯的方法
CN106939076A (zh) * 2011-12-19 2017-07-11 赢创德固赛有限公司 生产聚酯的方法
WO2015173310A1 (fr) * 2014-05-16 2015-11-19 Basf Se Production de polyamides par polymérisation hydrolytique suivie d'un traitement dans un malaxeur
CN106536595A (zh) * 2014-05-16 2017-03-22 巴斯夫欧洲公司 通过水解聚合和随后在捏合机中进行处理制备聚酰胺
KR20180018985A (ko) 2016-08-11 2018-02-22 주식회사 미래에스아이 스티렌-부타디엔 고무 용액과 표면 처리된 실리카의 혼합물로부터 습윤 마스터 배치의 제조방법
US11535705B2 (en) * 2018-01-24 2022-12-27 Sk Chemicals Co., Ltd. Polycarbonate ester and preparation method therefor
CN110195263A (zh) * 2019-06-20 2019-09-03 王维列 一种溶剂法生产再生纤维素纤维纺丝胶液的制备方法
US20210089920A1 (en) * 2019-09-20 2021-03-25 Axalta Coating Systems Ip Co., Llc Systems and methods for approximating a 5-angle color difference model
US11694364B2 (en) * 2019-09-20 2023-07-04 Axalta Coating Systems Ip Co., Llc Systems and methods for approximating a 5-angle color difference model

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