US20090306268A1 - Polyester Compositions Containing Metathesis Polymers with Reduced Recycle Color - Google Patents

Polyester Compositions Containing Metathesis Polymers with Reduced Recycle Color Download PDF

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US20090306268A1
US20090306268A1 US12/224,633 US22463307A US2009306268A1 US 20090306268 A1 US20090306268 A1 US 20090306268A1 US 22463307 A US22463307 A US 22463307A US 2009306268 A1 US2009306268 A1 US 2009306268A1
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composition
polymer
metathesis
unsaturated
aromatic polyester
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James Pawlow
William Hergenrother
Dan Graves
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Firestone Polymers LLC
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Firestone Polymers LLC
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Assigned to FIRESTONE POLYMERS, LLC reassignment FIRESTONE POLYMERS, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GRAVES, DAN, HERGENROTHER, WILLIAM L., PAWLOW, JAMES
Publication of US20090306268A1 publication Critical patent/US20090306268A1/en
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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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F232/04—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F232/06—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers

Definitions

  • This invention relates to aromatic polyester compositions that include unsaturated polymers prepared by metathesis polymerization.
  • Polyester resins such as poly(ethylene terephthalate) are commonly used to fabricate containers that are useful in food and beverage packaging. These resins, however, have limited packaging life, especially in the packaging of food and beverages that are sensitive to or degrade in the presence of oxygen.
  • these unsaturated polymers within the polyester composition leads to recycling difficulty. Namely, these compositions are not desirable for recycling because of the formation of color during the drying cycle. In particular, these compositions have suffered from the formation of red and yellow discoloration.
  • the present invention relates to a composition
  • a composition comprising the reaction product or a mixture of, (i) an aromatic polyester, and (ii) an unsaturated polymer having at least one terminal functional group, where said unsaturated polymer is formed by metathesis polymerization
  • the present invention also relates to a composition
  • a composition comprising the reaction, product of, or a mixture of, (i) an aromatic polyester resin; and (ii) an unsaturated polymer having at least one terminal functional group, where said unsaturated polymer is formed by metathesis polymerization.
  • the terminal functional group that is usable herein is a group selected from hydroxyl, carboxylic acid, ester, carbonate, cyclic carbonate, anhydride, cyclic anhydride, lactone, amine, amide, lactam, cyclic ether, ether, aldehyde, thiazoline, oxazoline, phenol, melamine, and mixtures thereof.
  • the terminal functional group is a group selected from hydroxyl, carboxylic acid, and ester, and mixtures thereof.
  • One or more embodiments of this invention are directed to an aromatic polyester resin composition that includes an unsaturated metathesis polymer having at least one terminal functional group.
  • the unsaturated polymer is prepared by employing any metathesis reaction techniques.
  • the unsaturated metathesis polymer is characterized by pendant vinyl group content of less than about 2%.
  • the unsaturated metathesis polymer is characterized by having about 5 to about 25 double bonds per 100 carbon atoms in the polymer chain.
  • the terminal functional group that is usable herein is a group selected from hydroxyl, carboxylic acid, ester, carbonate, cyclic carbonate, anhydride, cyclic anhydride, lactone, amine, amide, lactam, cyclic ether, ether, aldehyde, thiazoline, oxazoline, phenol, melamine, and mixtures thereof.
  • the terminal functional group is a group selected from hydroxyl, carboxylic acid, and ester, and mixtures thereof.
  • aromatic polyester resins derive from aromatic dicarboxylic acids and diols.
  • Exemplary dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether carboxylic acid, diphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, and mixtures thereof.
  • the polyesters may derive from derivatives of these acids such as dimethyl esters thereof.
  • Exemplary diols include ethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, cyclohexanedimethanol, tricyclodecanedimethanol, 2,2-bis (4-hydroxy ethoxy phenyl) propane, 4,4′-bis (hydroxy ethoxy) diphenyl sulfone, diethylene glycol and mixtures thereof.
  • aromatic polyesters examples include poly(alkylene terephthalate) resins such as poly(ethylene terephthalate), poly(butylene terephthalate), and poly(cyclohexane dimethylene terephthalate).
  • Others include poly(alkylene naphthalate) resins such as poly(ethylene naphthalate), poly(butylene naphthalate), and poly(cyclohexane dimethylene naphthalate).
  • the aromatic polyester resin may be characterized by an intrinsic viscosity that is in excess of 0.5 dl/g, in other embodiments in excess of 0.6 dl/g, and in other embodiments in excess of 0.7 dl/g, where the intrinsic viscosity is measured at 25° C. in a 50/50 blend of phenol and 1,1,2,2-tetrachloroethane.
  • the aromatic polyester resin may be characterized by an intrinsic viscosity that is less than 1.2 dl/g, in other embodiments less than 1.0 dl/g, and in other embodiments less than 0.95 dl/g.
  • the aromatic polyester resin may be characterized by a melt temperature that is in excess of 200° C., in other embodiments in excess of 220° C., and in other embodiments in excess of 230° C.
  • the aromatic polyester resins include those that are prepared from dimethyl terephthalate and ethylene glycol by a two-stage esterification process. Others include those prepared by direct esterification of a diacid with a diol or esterification of the diacid with ethylene oxide. Other methods for producing desirable resins for use in this invention are also known such as those methods described in U.S. Pat. No. 6,083,585, which is incorporated herein by reference.
  • the unsaturated polymers employed in the present invention are metathesis-synthesized polymers that have at least one or more terminal functional groups.
  • olefins such as cycloolefins and alpha, omega dienes
  • the metathesis reaction may be ring opening metathesis polymerization (ROMP), acyclic diene metathesis polymerization (ADMET), or the like.
  • metathesis-synthesized high molecular weight polymers are modified (e.g., molecular weight reduction) by employing metathesis catalysts to provide unsaturated polymers useful for practicing the present invention.
  • a functional olefin i.e., an olefin including one or more functional groups
  • the unsaturated polymers comprise one or more functional groups.
  • the resulting polymer has from about 5 to about 25 double bonds per 100 carbon atoms in the polymer chain.
  • the terminal functional group that is usable herein is a group selected from hydroxyl, carboxylic acid, ester, carbonate, cyclic carbonate, anhydride, cyclic anhydride, lactone, amine, amide, lactam, cyclic ether, ether, aldehyde, thiazoline, oxazoline, phenol, melamine, and mixtures thereof.
  • the terminal functional group is a group selected from hydroxyl, carboxylic acid, and ester, and mixtures thereof.
  • the metathesis catalyst includes a transition metal carbene complex.
  • Suitable transition metal carbene complexes include a positively charged metal center (e.g. in the +2, +4, or +6 oxidation state) that is penta- or hexa-coordinated.
  • Exemplary transition metals include transition metals from Groups 3 to 12 of the Periodic Table, according to IUPAC conventions.
  • the metathesis catalyst includes a ruthenium-based or osmium-based metathesis catalyst.
  • Any ruthenium-based or osmium-based metathesis catalyst that is effective for metathesis polymerization reactions can be used.
  • certain ruthenium and/or osmium-based catalysts are unaffected or only immaterially affected by the presence of certain advantageous functional groups present on the alkene.
  • the ruthenium-based or osmium-based metathesis catalysts includes carbene complexes of the type sometimes referred to as Grubbs catalysts.
  • Grubbs metathesis catalysts are described in U.S. Pat. Nos. 5,312,940, 5,342,909, 5,831,108, 5,969,170, 6,111,121, 6,211,391, 6,624,265, 6,696,597 and U.S. Published App. Nos. 2003/0181609 A1, 2003/0236427 A1, and 2004/0097745 A9, all of which are incorporated herein by reference.
  • Ru- or Os-based metathesis catalysts include compounds that can be represented by the formula
  • M includes ruthenium or osmium
  • L and L′ each independently include any neutral electron donor ligand
  • a and A′ each independently include an anionic substituent
  • R 3 and R 4 independently comprise hydrogen or an organic group, and includes an integer from o to about 5, or where two or more of R 3 , R 4 , L, L′, A, and A′ combine to form a bidentate substituent.
  • L and L′ independently include phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibnite, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, trizolidene, or imidazolidene groups, or L and L′ may together include a bidentate ligand.
  • L and/or L′ include an imidizolidene group that can be represented by the formulas
  • R 5 and R 6 independently include alkyl, aryl, or substituted aryl.
  • R 5 and R 6 independently include substituted phenyls, and in another embodiment, R 5 and R 6 independently include mesityl.
  • R 7 and R 8 include alkyl or aryl, or form a cycloalkyl, and in another embodiment, are both hydrogen, t-butyl, or phenyl groups. Two or more of R 5 , R 6 , R 7 and R 8 can combine to form a cyclic moiety.
  • imidazolidine ligands include 4,5-dihydro-imidazole-2-ylidene ligands.
  • a and A′ independently include halogen, hydrogen, C 1 -C 20 alkyl, aryl, C 1 -C 20 alkoxide, aryloxide, C 2 -C 20 alkoxycarbonyl, arylcarboxylate, C 1 -C 20 carboxylate, arylsulfonyl, C 1 -C 20 alkylsulfonyl, C 1 -C 20 alkylsulfinyl, each ligand optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy, or with a phenyl group that is optionally substituted with halogen, C 1 -C 5 alkyl, or C 1 -C 5 alkoxy, and A and A′ together may optionally include a bidentate ligand.
  • R 3 and R 4 include groups independently selected from hydrogen, C 1 -C 20 alkyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, aryloxy, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl and C 1 -C 20 alkylsulfinyl, each of R 3 and R 4 optionally substituted with C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy or with a phenyl group that is optionally substituted with halogen, C 1 -C 5 alkyl, or C 1 -C 5 alkoxy.
  • useful olefin monomers include those that will undergo a metathesis reaction, i.e. those that include at least one metathesis-active double bond.
  • the cycloolefins may be a cycloalkene or a cyclopolyene.
  • Suitable examples of acyclic monomers include dienes, alpha omega dienes, oligomers of olefins, and the like.
  • the cycloolefin includes a mixture of two or more cycloolefins that differ in ring size or in substituents, or a mixture of two or more isomers of cycloolefins. Any combination of two or more cycloolefins can be used that provides the desired polymer properties, as discussed below.
  • the mixture includes cyclooctadiene and cyclopentene, or in other embodiments 1,5-cyclooctadiene and cyclooctene.
  • cycloolefin that can participate in a ring-opening metathesis polymerization (ROMP) reaction may be used.
  • the cycloolefin may include one or more substituent groups and/or functional groups.
  • the cycloolefin may be a cycloalkene or a cyclopolyene.
  • the functional alkene which may also be referred to as a functionalizing agent, includes at least one metathesis-active double bond.
  • the acyclic alkene includes functional end-groups.
  • the alkene may be represented by the formula
  • the progress of the reaction can optionally be monitored by standard analytical techniques, or by monitoring the percent solids.
  • the metathesis reaction may optionally be terminated by adding a catalyst deactivator, such as ethyl vinyl ether.
  • the unsaturated metathesis polymer having at least one or more terminal functional groups employed in the present invention may be characterized by a relatively low pendant vinyl group content.
  • Pendant vinyl group refers to an alkenyl group along the polymer backbone with one point of attachment to the backbone exclusive of a terminal end group.
  • the polymer may include less than about 2%, in other embodiments less than about 1%, in other embodiments less than about 0.5%, and in other embodiments less than about 0.05% of vinyl groups or 1,2 configuration.
  • the unsaturated polymer is substantially devoid of pendant vinyl units where substantially devoid includes that amount or less pendant vinyl units that would otherwise have an appreciable impact on the polymer and/or blend of the invention. In one or more embodiments, the unsaturated polymer is devoid of pendant vinyl groups.
  • the melting point of the unsaturated polymer having at least one or more terminal functional groups may be from about minus ( ⁇ ) 40° C. to about (+) 50° C., in other embodiments from about minus 35° C. to about 40° C., and in yet other embodiments from about minus 30° C. to about 20° C.
  • the melting point of the polymer can be controlled by selecting the relative amounts of monomers.
  • the melting point of a copolymer prepared from cyclooctadiene and cyclopentene may vary from about minus ( ⁇ ) 30° C. to about (+) 40° C. as the mole fraction of pentene units in the copolymer decrease from about 0.3 to about zero percent, based upon the total moles of cyclooctadiene and cyclopentene.
  • the unsaturated polymer having at least one or more terminal functional groups may be characterized by a number average molecular weight (M n ) of at least about 0.5 kg/mole, in other embodiments at least about 1 kg/mole, in other embodiments at least about 1.5 kg/mole, and in other embodiments at least about 2.0 kg/mole.
  • M n number average molecular weight
  • the unsaturated polymer may be characterized by a number average molecular weight of less than about 100 kg/mole, in other embodiments less than about 80 kg/mole, in other embodiments less than about 60 kg/mole, and in other embodiments less than 40 kg/mole and in another embodiment, less than about 20 kg/mole.
  • the unsaturated polymer may be characterized by a molecular weight distribution (Mw/Mn) of from about 1.05 to about 2.5, in other embodiments from about 1.1 to about 2.0, and in other embodiments from about 1.2 to about 1.8.
  • Mw/Mn molecular weight distribution
  • Molecular weight may be determined by using standard GPC techniques with polystyrene standards.
  • the methathesis polymer having at least one or more terminal functional groups may be characterized by relatively low unsaturation.
  • the metathesis polymer contains from about 5 to about 25 double bonds per 100 carbon atoms, in other embodiments, the metathesis polymer contains from about 6 to about 20 double bonds per 100 carbon atoms, in other embodiments from about 7 to about 18 double bonds per 100 carbon atoms, and in other embodiments, the metathesis polymer contains from about 10 to about 15 double bonds per 100 carbon atoms in the polymer.
  • the metathesis polymers herein have a cis content of about greater than 10%; and in another embodiment, greater than 30%, and in another embodiment, greater than 50%.
  • the compositions can be prepared by mixing or blending of an aromatic polyester resin and the metathesis polymer having at least one or more terminal functional groups herein.
  • Techniques for mixing are known in the art, and this invention is not limited to the selection of a particular method.
  • the mixing occurs in a reactive extruder such as a twin-screw extruder.
  • the mixing or blending of the aromatic polyester resin and the metathesis polymer having at least one or more terminal functional groups can occur over a wide range of conditions. These conditions are selected such that substantially all of the functional groups attached to the metathesis polymer will be expected to react with the poly(ethylene terephthalate). In one or more embodiments, the mixing or blending can occur at a temperature of from about 230° C. to about 310° C. and in other embodiments from about 250° C. to about 290° C.
  • the residence time within the extruder is maintained for about 2 to about 6 minutes, and in other embodiments from about 3 to about 5 minutes.
  • the aromatic polyester resin and metathesis polymer having at least one or more terminal functional groups may be mixed or blended in the presence of catalysts, modifiers, heat stabilizers, antioxidants, colorants, crystallization nucleating agents, fillers, biodegradation accelerants or additional constituents that can be incorporated into the composition.
  • aromatic polyester compositions are known as described in U.S. Pat. No. 6,083,585, which is incorporated herein by reference.
  • the aromatic polyester compositions of this invention include from about 0.05 to about 0.15 weight percent transition metal catalyst based upon the weight of the metathesis polymer. In other embodiments, the composition includes from about 0.07 to about 0.12 weight percent, and in other embodiments from about 0.09 to about 0.11 weight percent based upon the weight of the metathesis polymer.
  • the aromatic polyester compositions may include or be modified by condensation branching or coupling agents that alter the intrinsic viscosity of the compositions.
  • the compositions include the reaction product between the branching agent and the aromatic polyester and/or metathesis polymer having at least one or more terminal functional groups.
  • These agents may include polycondensate branching agents.
  • these branching agents may include trimellitic anhydride, aliphatic dianhydrides and aromatic dianhydrides.
  • pyromellitic dianhydride i.e., benzene 1,2,4,5-tetracarboxylicacid dianhydrides is employed.
  • the composition including the aromatic polyester resin and metathesis polymer having at least one or more terminal functional groups herein are prepared as concentrates or masterbatches that can be subsequently added to other thermoformable resins (e.g., aromatic polyester resins) for use in preparing particular articles.
  • the composition of this invention may include at least 1%, in other embodiments at least 5%, and in other embodiments at least 10% by weight unsaturated metathesis polymer having at least one or more terminal functional groups herein based upon the total weight of the total composition.
  • these concentrates or masterbatch pellets include less than 30%, and in other embodiments less than 20%, and in other embodiments less than 15% by weight metathesis polymer based upon the total weight of the composition.
  • the compositions include at least 0.05%, in other embodiments at least 0.5%, and in other embodiments at least 0.9% by weight metathesis polymer based upon the total weight of the composition.
  • the thermoformable composition includes less than 5%, in other embodiments less than 3%, and in other embodiments less than 1.5% by weight based upon the total weight of the composition.
  • the composition of the invention includes the reaction product between an aromatic polyester resin and a metathesis polymer having at least one or more terminal functional groups herein.
  • the compositions of this invention include an aromatic polyester resin matrix having dispersed therein domains of the metathesis polymer.
  • the characteristics, especially the size, of these metathesis polymer domains can be adjusted based upon mixing conditions and functionality of the metathesis polymer. It is expected that in one or more embodiments, the metathesis polymer domains are characterized by an expected average diameter of less than 400 nanometers, in other embodiments less than an expected 300 nanometers, and in other embodiments less than an expected 200 nanometers. The size and stability of the domains formed are expected to be controlled and stabilized by the reaction and attachment of the functional metathesis polymer to the aromatic polyester.
  • compositions of this invention are advantageously thermoformable, and therefore they can be used in the various thermoforming techniques that are known such as, but not limited to, injection molding, blow molding, and compression molding. In one or more embodiments, the compositions of this invention can also be extruded.
  • compositions can be used to fabricate packaging walls and packaging articles.
  • these packaging articles include those used with perishable foods and beverages.
  • compositions of one or more embodiments of this invention are advantageously recyclable where formation of color is reduced.
  • a further advantage would be expected by the reaction and attachment of the functional metathesis polymer to the aromatic polyester substantially reducing the leaching or migration of the rubber polymer away from the polyester.
  • the resultant hydroxyl terminated polypentenamer is expected to be useful in preparing compositions with aromatic polyesters.
  • a batch mixture was charged consisting of 1185 mL (996 g, 9.0 mol) of degassed cyclooctene, 560 mL (497 g, 4.6 mol) degassed 1,5-cyclooctadiene, and 60 mL (65.5 g, 0.38 mol) degassed cis-1,4-diacetoxy-2-butene.
  • the mixture was stirred and heated to 50° C.
  • a solution of 0.42 g (0.50 mmol) Grubbs' 2 nd generation ruthenium metathesis catalyst in 10 mL dry, degassed toluene was prepared under inert atmosphere and added to the monomer mixture.
  • the terminal functionalized polymers of Examples 2 and 3 are expected to be useful in preparing compositions with aromatic polyesters.

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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)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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US12/224,633 US20090306268A1 (en) 2006-03-01 2007-03-01 Polyester Compositions Containing Metathesis Polymers with Reduced Recycle Color
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US11390709B2 (en) 2017-09-29 2022-07-19 Zeon Corporation Liquid copolymer formed by ring-opening copolymerization of cyclopentene, crosslinkable composition, and crosslinked rubber object
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WO2007100891A1 (en) 2007-09-07
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