WO2009127009A1 - Condensation polymers - Google Patents

Condensation polymers Download PDF

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Publication number
WO2009127009A1
WO2009127009A1 PCT/AU2009/000477 AU2009000477W WO2009127009A1 WO 2009127009 A1 WO2009127009 A1 WO 2009127009A1 AU 2009000477 W AU2009000477 W AU 2009000477W WO 2009127009 A1 WO2009127009 A1 WO 2009127009A1
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WIPO (PCT)
Prior art keywords
acid
hydroxy
poly
cyclic ester
nylon
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PCT/AU2009/000477
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French (fr)
Inventor
Florian Hans Maximilian Graichen
Michael Shane O'shea
Gary Peeters
Andrew Charles Warden
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
Grains Research And Development Corporation
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Priority claimed from AU2008901955A external-priority patent/AU2008901955A0/en
Application filed by Commonwealth Scientific And Industrial Research Organisation, Grains Research And Development Corporation filed Critical Commonwealth Scientific And Industrial Research Organisation
Publication of WO2009127009A1 publication Critical patent/WO2009127009A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08Lactones or lactides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds

Definitions

  • the present invention relates in general to condensation polymers.
  • the invention relates to aliphatic condensation polymers having modified properties
  • Condensation polymers such as polyesters and polyamides may be prepared with a diverse array of physical and chemical properties.
  • condensation polymers may vary widely in their stiffness, hardness, elasticity, tensile strength, density, and may or may not be susceptible to biodegradation.
  • aliphatic condensation polymers present their own unique physical and chemical properties.
  • aliphatic polyesters are known to exhibit good biodegradability.
  • aliphatic condensation polymers can lack the physical and/or chemical properties required for use in certain applications.
  • polylactic acid has relatively poor flexibility and its use in film based applications (e.g. as a packaging material) is limited.
  • a number of techniques for improving the physical and/or chemical properties of aliphatic condensation polymers have been developed.
  • specialty monomers that can influence the physical and/or chemical properties of the polymer may be used in conjunction with the conventional monomers during the condensation polymerisation manufacturing process.
  • deriving new and improved properties of condensation polymers in this way necessarily requires the use of rather specialised condensation polymerisation equipment.
  • the present invention provides a method of preparing a polymer composition, the method comprising melt mixing an aliphatic condensation polymer with a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I):
  • R is an optionally substituted aliphatic hydrocarbon having 3 or more carbon atoms.
  • the resulting modified condensation polymer includes as part its polymeric backbone the ⁇ -oxy carbonyl moiety of a general formula (T).
  • T general formula (T)
  • the presence of the moiety as part of the polymer backbone is believed to impart new and/or improved properties to the modified condensation polymer.
  • the present invention further provides a method for modifying an aliphatic condensation polymer, the method comprising melt mixing the condensation polymer with a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ce-oxy carbonyl moiety of general formula (I).
  • the methods of the invention can advantageously be performed using conventional melt mixing equipment known in the art.
  • the methods will be performed by introducing the cyclic ester and the condensation polymer individually or collectively into the appropriate melt mixing equipment.
  • the cyclic ester might be introduced to condensation polymer already in a molten state, or a mixture of the cyclic ester and the condensation polymer may be subjected to melt mixing.
  • the cyclic ester might also be provided in the form of a composition such as a masterbatch or concentrate which is subsequently let down into an aliphatic condensation polymer to be modified.
  • the composition will generally comprise the cyclic ester and one or more polymers (commonly referred to as a carrier polymer(s)).
  • the carrier polymer may be the same or different to the condensation polymer that is to be modified.
  • the carrier polymer(s) is an aliphatic condensation polymer.
  • the composition may be a physical blend of the cyclic ester and one or more carrier polymers, and/or may itself be prepared by melt mixing the cyclic ester with one or more carrier polymers.
  • the present invention therefore also provides a composition for modifying an aliphatic condensation polymer, the composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I), and/or a product formed by melt mixing a composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I).
  • the polymer composition comprises an aliphatic condensation polymer and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I) and/or a product formed by melt mixing a composition comprising an aliphatic condensation polymer and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I).
  • Aliphatic condensation polymers modified in accordance with the invention have been found to exhibit new and/or improved properties such as improved flexibility relative to the condensation polymer prior to being modified.
  • the cyclic esters used in accordance with the invention can advantageously be prepared using hydroxycarboxylic acids, a renewable resource that can be derived from plants and animals.
  • condensation polymer is intended to mean a polymer that has been formed via a condensation or step-wise polymerisation reaction.
  • condensation polymers include polyesters, polyamide and copolymers thereof.
  • the condensation polymers used are polyesters, polyamides, and copolymers thereof.
  • Condensation polymers used in accordance with the invention are "aliphatic condensation polymers".
  • aliphatic condensation polymers is meant that the polymer backbone does not incorporate an aromatic moiety.
  • polyethylene terephthalate i.e. PET
  • PET polyethylene terephthalate
  • polymer backbone is meant the main structure of the polymer on to which substituents may be attached.
  • the main structure of the polymer may be linear or branched.
  • the condensation polymers may also be acyclic (i.e. where the polymer backbone does not incorporate a cyclic moiety). Although the polymer backbone of the aliphatic condensation polymers will not incorporate an aromatic moiety (and possibly not a cyclic moiety), an aromatic or cyclic moiety may nonetheless be present in a position that is pendant from the polymer backbone. However, the aliphatic condensation polymers used in accordance with the invention will not generally comprise a pendant aromatic or cyclic moiety.
  • Aliphatic polyesters that may be used in the invention include homo- and copolymers of ⁇ oly(hydroxyalkanoates) and homo- and copolymers of those aliphatic polyesters derived from the reaction product of one or more alkyldiols with one or more alkyldicarboxylic acids (or acyl derivatives). Miscible and immiscible blends of aliphatic polyesters may also be used.
  • One class of aliphatic polyester includes poly(hydroxyalkanoates) derived by condensation or ring-opening polymerization of hydroxycarboxylic acids, or derivatives thereof.
  • Suitable poly(hydroxyalkanoates) may be represented by the formula H(O — R a — C(O) — ) n OH, where R a is an alkylene moiety that may be linear or branched and n is a number from 1 to 20, preferably 1 to 12.
  • R a may further comprise one or more caternary (i.e. in chain) ether oxygen atoms.
  • the R a group of the hydroxycarboxylic acids is such that the pendant hydroxyl group is a primary or secondary hydroxyl group.
  • Useful poly(hydroxyalkanoates) include, for example, homo- and copolymers of poly(3- hydroxybutyrate), poly(4-hydroxybutyrate), poly(3-hydroxyvalerate), poly(lactic acid) (also known as polylactide), poly(3-hydroxypropanoate), poly(4-hydropcntanoate), ⁇ oly(3- hydroxypentanoate), poly(3-hydroxyhexanoate), poly(3-hydroxyheptanoate), poly(3- hydroxyoctanoate), polydioxanone, and polycaprolactone, polyglycolic acid (also known as polyglycolide).
  • polyglycolic acid also known as polyglycolide
  • Copolymers of two or more of the above hydroxycarboxylic acids may also be used, for example, to provide for poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polyClactate-co-S-hydroxypropanoate) and poly ⁇ lycolide-co-p-dioxanone). Blends of two or more of the poly(hydroxyalkanoates) may also be used.
  • a further class of aliphatic polyester includes those aliphatic polyesters derived from the reaction product of one or more alkyldiols with one or more alkyldicarboxylic acids (or acyl derivatives). Such polyesters may have the general formula (II):
  • R b and R c each independently represent an alkylene moiety that may be linear or branched having from 1 to 20, preferably 1 to 12 carbon atoms, and p is a number such that the ester is polymeric, and is preferably a number such that the molecular weight of the aliphatic polyester is 10,000 to 300,000, more preferably from about 30,000 to 200,000.
  • Each m and n is independently 0 or 1.
  • R b and R c may further comprise one or more caternary (i.e. in chain) ether oxygen atoms.
  • aliphatic polyesters include those homo- and copolymers derived from (a) one or more of the following diacids (or derivative thereof): succinic acid, adipic acid, 1,12 dicarboxydodecane, fumaric acid, and maleic acid and (b) one of more of the following diols: ethylene glycol, polyethylene glycol, 1,2-propane diol, 1,3-propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and polypropylene glycol, and (c) optionally a small amount, e.g. 0.5-7.0 mole % of a polyol with a functionality greater than two such as glycerol, or pentaerythritol.
  • diacids or derivative thereof
  • succinic acid succin
  • Such aliphatic polyesters may include polybutylenesuccinate homopolymer, polybutylene adipate homopolmer, polybutyleneadipate-succinate copolymer, polyethylenesuccinate- adipate copolymer, polyethylene adipate homopolymer.
  • Common commercially available aliphatic polyesters include polylactide, polyglycolide, polylactide-co-glycolide, poly(L-lactide-co-trimethylene carbonate), poly(dioxanone), poly(butylene succinate), and poly(butylene adipate).
  • Blends of two or more aliphatic polyesters may also be used in accordance with the invention.
  • Aliphatic polyamides that may be used in the invention include those characterised by the presence of recurring carbonamide groups that form part of the polymer backbone and which are separated from one another by at least two aliphatic carbon atoms. Suitable aliphatic polyamides therefore include those having recurring units represented by general formulae (III) or (IV):
  • R d and R e are the same or different and are each independently alkylene groups of at least two carbon atoms, for example alkylene having about two to about 20 carbon atoms, preferably alkylene having about two to about 12 carbon atoms.
  • poly(tetramethylene adipamide) (nylon 4,6); pory(hexamethylene adipamide) (nylon 6,6); poly(hexamethylene azelamide) (nylon 6,9); poly(hexamethylene sebacamide) (nylon 6,10); poly(heptamethylene pimelamide) (nylon 7,7); poly(octamethylene suberamide) (nylon 8,8); pory(nonamethylene azelamide) (nylon 9,9); poly(decamethylene azelamide) (nylon 10,9); and the like.
  • polyamides are also those formed by polymerization of alkyl amino acids and derivatives thereof (e.g. lactams) and include poly(4-aminobutyric acid) (nylon 4); poly(6- aminohexanoic acid) (nylon 6); poly(7-amino-heptanoic acid) (nylon 7); poly(8- aminoocatanoic acid) (nylon 8); poly(9-aminononanoic acid) (nylon 9); poly(10- aminodecanoic acid) (nylon 10); poly(ll-aminoundecanoic acid) (nylon 11); poly(12- aminododecanoic acid) (nylon 12); and the like.
  • Blends of two or more aliphatic polyamides may also be used in accordance with the invention.
  • cyclic ester is intended to mean a cyclic molecule having at least one ring (or cycle) within its molecular structure that contains an ester moiety that forms part of that cycle.
  • the cyclic ester has at least two ester moieties that form part of its cycle.
  • cyclic esters are commonly referred to as macrocyclic oligoesters.
  • cyclic esters used in accordance with the invention comprise as part of their cycle an ⁇ -oxy carbonyl moiety of general formula (I):
  • R is an optionally substituted aliphatic hydrocarbon having three or more carbon atoms.
  • R in general formula (I) is an optionally substituted aliphatic hydrocarbon having three or more carbon atoms.
  • aliphatic hydrocarbon is meant a non-aromatic hydrocarbon.
  • the hydrocarbon group R may also be an acyclic hydrocarbon (i.e. a non-cyclic hydrocarbon).
  • the hydrocarbon group R may be a linear or branched alkyl, alkenyl, or alkynyl group.
  • the hydrocarbon group R may be saturated or unsaturated. Where the hydrocarbon group R is unsaturated, it may be mono- or poly-unsaturated, and include both cis- and trans- isomers.
  • the hydrocarbon R will generally have 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 6 to 20 carbon atoms.
  • the hydrocarbon R may be substituted, for example with a hetero atom containing moiety and/or an aromatic or cyclic moiety. In some embodiments the R group is not substituted.
  • the modified condensation polymers in accordance with the invention can advantageously undergo reaction through the reactive functional groups within or substituted on the hydrocarbon R.
  • the hydrocarbon group R is unsaturated
  • the unsaturated bonds may take part in crosslinking reactions (i.e. oxidative crosslinking similar to that which occurs in alkyd paints, or free radical mediated reactions), and free radical mediated grafting reactions.
  • Crosslinking and grafting reactions may also be conducted through reactive functional group substituents on the hydrocarbon group R.
  • Providing the hydrocarbon group R with one or more reactive functional groups can advantageously enable organic or inorganic moieties to be tethered to the polymer backbone through reaction of the moieties with such groups.
  • the organic or inorganic moieties may be conveniently tethered to the R group of the cyclic ester prior to it being melt mixed with the aliphatic condensation polymer, or tethered to the R group after the cyclic ester has been melt mixed with the aliphatic condensation polymer.
  • the R group of general formula (I) is an aliphatic hydrocarbon comprising conjugated double and/or triple bonds.
  • conjugation is in the form of an yne-yne, ene-ene, yne-yne-yne, yne-yne-ene-, ene-yne-yne or yne-ene-yne moiety.
  • alkyl used either alone or in compound words denotes straight chain, branched or cyclic alkyl, for example C 1-40 alkyl, or C 1-20 or C 1-10 .
  • straight chain and branched alkyl include methyl, ethyl, ⁇ -propyl, isopropyl, ra-butyl, sec- butyl, t-butyl, n-pentyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, hexyl, 4-methylpentyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3- dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2- trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 1-methylhexy
  • cyclic alkyl examples include mono- or polycyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Where an alkyl group is referred to generally as "propyl", butyl” etc, it will be understood that this can refer to any of straight, branched and cyclic isomers where appropriate. An alkyl group may be optionally substituted by one or more optional substituents as herein defined.
  • alkenyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon to carbon double bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined, for example C 2-40 alkenyl, or C 2-20 or C 2-10 .
  • alkenyl is intended to include propenyl, butylenyl, pentenyl, hexaenyl, heptaenyl, octaenyl, nonaenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nondecenyl, eicosenyl hydrocarbon groups with one or more carbon to carbon double bonds.
  • alkenyl examples include vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1 -pentenyl, cyclopentenyl, 1-methyl- cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl, 1,4- pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloh
  • alkynyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon-carbon triple bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined, for example, C 2-40 alkenyl, or C 2-20 or C 2-10 .
  • alkynyl is intended to include propynyl, butylynyl, pentynyl, hexaynyl, heptaynyl, octaynyl, nonaynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nondecynyl, eicosynyl hydrocarbon groups with one or more carbon to carbon triple bonds.
  • alkynyl examples include ethynyl, 1 -propynyl, 2-propynyl, and butynyl isomers, and pentynyl isomers.
  • An alkynyl group may be optionally substituted by one or more optional substituents as herein defined.
  • An alkenyl group may comprise a carbon to carbon triple bond and an alkynyl group may comprise a carbon to carbon double bond (i.e. so called ene-yne or yne-ene groups).
  • aryl denotes any of single, polynuclear, conjugated and fused residues of aromatic hydrocarbon ring systems.
  • aryl include phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl, fluorenyl, pyrenyl, idenyl, azulenyl, chrysenyl.
  • Preferred aryl include phenyl and naphthyl.
  • An aryl group may be optionally substituted by one or more optional substituents as herein defined.
  • alkylene As used herein, the terms “alkylene”, “alkenylene”, and “arylene” are intended to denote the divalent forms of “alkyl”, “alkenyl”, and “aryl”, respectively, as herein defined.
  • optionally substituted is taken to mean that a group may or may not be substituted or fused (so as to form a condensed polycyclic group) with one, two, three or more of organic and inorganic groups (i.e. the optional substituent) including those selected from: alkyl, alkenyl, alkynyl, carbocyclyl, aryl, heterocyclyl, heteroaryl, acyl, aralkyl, alkaryl, alkheterocyclyl, alkheteroaryl, alkcarbocyclyl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, halocarbocyclyl, haloheterocyclyl, haloheteroaryl, haloacyl, haloaryalkyl, hydroxy, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, hydroxycarbocyclyl, hydroxy
  • a group is optionally substituted with a reactive functional group or moiety.
  • reactive functional groups or moieties include epoxy, anhydride, cyclic ester (e.g. lactone or higher cyclic oligoester), cyclic amide (e.g. lactam or higher cyclic oligoamide), oxazoline and carbodimide.
  • a group is optionally substituted with a polymer chain.
  • An example of such a polymer chain includes a polyether chain.
  • Preferred optional substituents include the aforementioned reactive functional groups or moieties, polymer chains and alkyl, (e.g. C 1-6 alkyl such as methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), hydroxyalkyl (e.g. hydroxymethyl, hydroxyethyl, hydroxypropyl), alkoxyalkyl (e.g.
  • alkoxy e.g. C 1-6 alkoxy such as methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy
  • halo trifluoromethyl, trichloromethyl, tribromomethyl, hydroxy, phenyl (which itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyC 1-6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino)
  • benzyl wherein benzyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyC 1-6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl etc) alkoxy (e.g. C 1-6 alkoxy such as methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cycl
  • C 1-6 alkyl such as methylamino, ethylamino, propylamino etc
  • dialkylamino e.g. C 1-6 alkyl, such as dimethylaniino, diethylamino, dipropylamino
  • acylamino e.g.
  • phenylamino (wherein phenyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy hydroxyC 1-6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino), nitro, formyl, -C(O)-alkyl (e.g. C 1-6 alkyl, such as acetyl), O-C(O)-alkyl (e.g.
  • C 1- 6 alkyl such as acetyloxy
  • benzoyl wherein the phenyl group itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy hydroxyC 1-6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino
  • C 1-6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl ester
  • C0 2 phenyl wherein phenyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyl C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino
  • CONH 2 CONHphenyl (wherein phenyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyl C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino)
  • CONHbenzyl wherein benzyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy hydroxy
  • C 1-6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl amide) CONHdialkyl (e.g. C 1-6 alkyl) aminoalkyl (e.g., HN C 1-6 alkyl-, C 1-6 alkylHN-C 1-6 alkyl- and (C 1-6 alkyl) 2 N-C 1-6 alkyl-), thioalkyl (e.g., HS C 1-6 alkyl-), carboxyalkyl (e.g., HO 2 CC 1-6 alkyl-), carboxyesteralkyl (e.g., C 1-6 alkylO 2 CC 1-6 alkyl-), amidoalkyl (e.g., H 2 N(O)CC 1-6 alkyl-, H(C 1-6 alkyl)N(O)CC 1-6 alkyl-), formylalkyl (e.g., OHCC 1-6 alkyl-), acylalkyl
  • the aliphatic hydrocarbon group R is optionally substituted with a cyclic ester, cyclic amide, or polyether chain.
  • halogen denotes fluorine, chlorine, bromine or iodine (fluoro, chloro, bromo or iodo). Preferred halogens are chlorine, bromine or iodine.
  • carbocyclyl includes any of non-aromatic monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3-20 (e.g. C 3-1O or C 3-8 ).
  • the rings may be saturated, e.g. cycloalkyl, or may possess one or more double bonds (cycloalkenyl) and/or one or more triple bonds (cycloalkynyl).
  • Particularly preferred carbocyclyl moieties are 5-6-membered or 9-10 membered ring systems.
  • Suitable examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclooctatetraenyl, indanyl, decalinyl and indenyl.
  • heterocyclyl when used alone or in compound words includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3-20 (e.g. C 3-10 or C 3-8 ) wherein one or more carbon atoms are replaced by a heteroatom so as to provide a non-aromatic residue.
  • Suitable heteroatoms include O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • the heterocyclyl group may be saturated or partially unsaturated, i.e. possess one or more double bonds. Particularly preferred heterocyclyl are 5-6 and 9-10 membered heterocyclyl.
  • heterocyclyl groups may include azridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl, thietanyl, 2H-pyrrolyl, pyrrolidinyl, pyrrolinyl, piperidyl, piperazinyl, morpliolinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, thiomorpholinyl, dioxanyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyrrolyl, tetrahydrothiophenyl, pyrazolinyl, dioxalanyl, thiazolidinyl, isoxazolidinyl, dihydropyranyl, oxazinyl, thiazinyl, thiomorpholinyl, oxathianyl, dithi
  • heteroaryl includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, wherein one or more carbon atoms are replaced by a heteroatom so as to provide an aromatic residue.
  • Preferred heteroaryl have 3-20 ring atoms, e.g. 3-10.
  • Particularly preferred heteroaryl are 5-6 and 9-10 membered bicyclic ring systems.
  • Suitable heteroatoms include, O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • heteroaryl groups may include pyridyl, pyrrolyl, thienyl, imidazolyl, furanyl, benzothienyl, isobenzothienyl, benzofuranyl, isobenzofuranyl, indolyl, isoindolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, quinolyl, isoquinolyl, phthalazinyl, 1,5-naphthyridinyl, quinozalinyl, quinazolinyl, quinolinyl, oxazolyl, thiazolyl, isothiazolyl, isoxazolyl, triazolyl, oxadialzolyl, oxatriazolyl, triazinyl, and furazanyl.
  • Preferred acyl includes C(O)-R X , wherein R x is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • R x is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • Examples of acyl include formyl, straight chain or branched alkanoyl (e.g.
  • C 1-20 such as, acetyl, propanoyl, butanoyl, 2-methylpropanoyl, pentanoyl, 2,2- dimethylpropanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl and icosanoyl; cycloalkylcarbonyl such as cyclopropylcarbonyl cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexylcarbonyl; aroyl such as benzoyl, toluoyl and naphthoyl; aralkanoyl
  • phenylacetyl phenylpropanoyl, phenylbutanoyl, phenylisobutylyl, phenylpentanoyl and phenylhexanoyl
  • naphthylalkanoyl e.g. naphthylacetyl, naphthylpropanoyl and naplithylbutanoyl
  • aralkenoyl such as phenylalkenoyl (e.g.
  • phenylpropenoyl e.g., phenylbutenoyl, phenylmethacryloyl, phenylpentenoyl and phenylhexenoyl and naphthylalkenoyl (e.g.
  • aryloxyalkanoyl such as phenoxyacetyl and phenoxypropionyl
  • arylthiocarbamoyl such as phenylthiocarbamoyl
  • arylglyoxyloyl such as phenylglyoxyloyl and naphthylglyoxyloyl
  • arylsulfonyl such as phenylsulfonyl and napthylsulfonyl
  • heterocycliccarbonyl heterocyclicalkanoyl such as thienylacetyl, thienylpropanoyl, thienylbutanoyl, thienylpentanoyl, thienylhexanoyl, thiazolylacetyl, thiadiazolylacetyl and tetrazolylacetyl
  • sulfoxide refers to a group -S(O)R y wherein R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl. Examples of preferred R y include C 1-20 alkyl, phenyl and benzyl.
  • sulfonyl refers to a group S(O) 2 -R y , wherein R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl.
  • R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl.
  • R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl.
  • R y is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl.
  • R y include Ci -2 oalkyl, phenyl and benzyl.
  • sulfonamide refers to a group S(O)NR y R y wherein each R y is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • R y is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • R y include C 1- 20 alkyl, phenyl and benzyl.
  • at least one R y is hydrogen.
  • both R y are hydrogen.
  • amino is used here in its broadest sense as understood in the art and includes groups of the formula NR R wherein R A and R B may be any independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl. R A and R B , together with the nitrogen to which they are attached, may also form a monocyclic, or polycyclic ring system e.g. a 3-10 membered ring, particularly, 5-6 and 9- 10 membered systems. Examples of “amino” include NH 2 , NHalkyl (e.g. C 1-2 oalkyl), NHaryl (e.g.
  • NHaralkyl e.g. NHbenzyl
  • NHacyl e.g. NHC(O)C 1-20 alkyl, NHC(O)phenyl
  • Nalkylalkyl wherein each alkyl, for example C 1-20 , may be the same or different
  • 5 or 6 membered rings optionally containing one or more same or different heteroatoms (e.g. O, N and S).
  • amido examples include C(O)NH 2 , C(O)NHalkyl (e.g. C 1-2O alkyl), C(O)NHaryl (e.g.
  • C(O)NHphenyl C(O)NHaralkyl (e.g. C(O)NHbenzyl), C(O)NHacyl (e.g.
  • carboxy ester is used here in its broadest sense as understood in the art and includes groups having the formula CO 2 R 2 , wherein R z may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.
  • R z may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.
  • Examples of carboxy ester include CO 2 C 1-20 alkyl, CO 2 aryl (e.g.. CO 2 phenyl), CO 2 aralkyl (e.g. CO 2 benzyl).
  • heteroatom refers to any atom other than a carbon atom which may be a member of a cyclic organic group.
  • heteroatoms include nitrogen, oxygen, sulfur, phosphorous, boron, silicon, selenium and tellurium, more particularly nitrogen, oxygen and sulfur.
  • the cyclic ester used in accordance with the invention has at least two ester moieties that form part of its cycle.
  • the carbonyl group of the ⁇ -oxy carbonyl moiety of general formula (I) will in effect provide for one of these ester moieties, and the at least one other ester moiety will be provided by at least one other condensed moiety of a hydroxycarboxylic acid.
  • This at least one further condensed hydroxycarboxylic acid residue may be the same or different to the ⁇ -oxy carbonyl moiety of general formula (I), and will complete the cycle of the cyclic ester as represented by the dashed lines in general formula (I).
  • a cyclic ester suitable for use in accordance with the invention might have a cyclic structure that is formed from the condensed moieties of at least two ⁇ -hydroxycarboxylic acids of general formula (V), or one or more ⁇ -hydroxycarboxylic acids of general formula (V) and one or more other hydroxycarboxylic acids.
  • the general structure of a cyclic ester of this type may be conveniently represented by general formula (VI): An 1 -Bn 2 -An" -Bn 4 An M — Bn 1 (VI)
  • A is a condensation residue of an ce-hydroxycarboxylic acid of general structure (V)
  • B is the condensation residue of a hydroxycarboxylic acid
  • each A and each B may be the same or different
  • each n may be 0 or a positive integer
  • i is a positive integer of the series 1, 2, 3, i, wherein n 1 >1 and n*+n 2 >2.
  • the cyclic ester of general formula (VI) can therefore be seen to represent a macrocyclic oligoester.
  • cyclic ester of general formula (VI) serves merely to illustrate the variety of cyclic structures that may be formed in the preparation of cyclic esters.
  • the cycle size of a cyclic ester may vary depending upon how the cyclic ester is made and from what hydroxycarboxylic acid it is made from.
  • a cyclic ester might also comprise a mixture of different cycle compositions and cycle sizes.
  • the cyclic esters used in accordance with the invention require at least two ester moieties that form part of its cycle.
  • the ester moieties will generally be joined with in the cycle by one or more carbon atoms.
  • the number of ester moieties that may form part of the cycle there will generally be no more than about six of such moieties.
  • the cyclic ester might be a dilactone, trilactone, tetralactone, pentalactone, hexalactone, or mixture thereof.
  • cyclic ester In view of the complexities associated with defining the specific composition of a cyclic ester, it can often be more convenient to refer to the cyclic ester in terms of it being formed from the condensed residue(s) of a particular hydroxycarboxylic acid(s).
  • the cyclic ester used in accordance with the invention comprises as part of its cycle the condensed residue of at least one a- hydroxycarboxylic acid of general formula (V).
  • the cyclic ester used in accordance with the invention comprises as part of its cycle the condensed residue of at least one a- hydroxycarboxylic acid of general formula (V) and at least one other hydroxycarboxylic acid.
  • the cyclic ester used in accordance with the invention comprises as part of its cycle the condensed residue of at least one a- hydroxycarboxylic acid of general formula (V) and at least one ce-hydroxycarboxylic acid of general formula (VII):
  • R 1 is an optionally substituted aliphatic hydrocarbon.
  • fatty acids of general formula (V) will generally undergo condensation reactions with itself or other hydroxycarboxylic acids to at least form a dilactone.
  • the cyclic ester comprises a dilactone formed through the condensation of an ce-hydroxycarboxylic acid of a general formula (V).
  • the cyclic ester comprises a dilactone formed through the condensation of an ⁇ -hydroxycarboxylic acid of general formula (V) and another hydroxycarboxylic acid.
  • the cyclic ester comprises a dilactone formed through the condensation of an ⁇ -hydroxycarboxylic acid of general formula (V) and an a- hydroxycarboxylic acid of general formula (VII).
  • the cyclic ester used in accordance with the invention comprises a dilactone of general formula (VIII):
  • R and R are the same or different and are as hereinbefore defined.
  • R 1 will generally be an aliphatic hydrocarbon having
  • R 1 may be linear or branched, saturated or unsaturated. Where the hydrocarbon is unsaturated, it may be mono- or poly-unsaturated, and includes both cis- and trans-isomers.
  • the hydrocarbon group R 1 may be a linear or branched alkyl, alkenyl, or alkynyl group.
  • R 1 may also be an acyclic hydrocarbon (i.e. a non-cyclic hydrocarbon). Accordingly, R 1 may be the same or different from R.
  • the hydrocarbon R 1 may be substituted, for example with a hetero atom containing moiety and/or an aromatic or cyclic moiety. In some embodiments the R 1 group is not substituted.
  • Cyclic esters suitable for use in accordance with the invention can advantageously be prepared in a similar manner.
  • cyclic esters can be prepared by subjecting an ce-hydroxycarboxylic acid of general formula (V), optionally together with one or more different hydroxycarboxylic acids, to heat under vacuum, or by using several methods described in the literature. (Journal of Biomedical Materials Research Part A, Volume 80A, Issue 1, pp 55-65, Polymer Preprints 2005, 46 (2), 1040, Polymer Preprints 2005 (46 (2), 1006).
  • Cyclic esters suitable for use in accordance with the invention may be conveniently prepared using a variety of ⁇ -hydroxycarboxylic fatty acids of general formula (V).
  • ⁇ -hydroxycarboxylic acids of general formula (V) include ⁇ -hydroxy valeric acid, ⁇ -hydroxy caproic acid, ⁇ -hydroxy caprylic acid, ⁇ -hydroxy pelargonic acid, ⁇ - hydroxy capric acid, ⁇ -hydroxy lauric acid, ⁇ -hydroxy mytistic acid, ⁇ -hydroxy palmitic acid, ⁇ -hydroxy margaric acid, ⁇ -hydroxy stearic acid, ⁇ -hydroxy arachidic acid, ⁇ - hydroxy behenic acid, ⁇ -hydroxy lignoceric acid, ⁇ -hydroxy cerotic acid, ⁇ -hydroxy carboceric acid, ⁇ -hydroxy montanic acid, ⁇ -hydroxy melissic acid, ⁇ -hydroxy lacceroic acid, ⁇ -hydroxy ceromelissic acid, ⁇ -hydroxy geddic acid, ⁇ -hydroxy
  • melt mixing can be performed using methods well known in the art.
  • melt mixing may be achieved using continuous extrusion equipment such as twin screw extruders, single screw extruders, other multiple screw extruders and Farell mixers.
  • Semi-continuous or batch processing equipment may also be used to achieve melt mixing. Examples of such equipment include injection moulders, Banbury mixers and batch mixers. Static melt mixing equipment may also be used.
  • the polymer composition resulting from the melt mixing process will therefore comprise modified aliphatic condensation polymer having the ⁇ -oxy moiety of general fo ⁇ iiula (I) incorporated as part of its polymeric backbone.
  • the polymer composition may also comprise a proportion of cyclic ester that has not undergone reaction with the aliphatic condensation polymer and/or polymer that has formed through ring opening polymerisation of the cyclic ester.
  • ⁇ -oxy moiety of general formula (I) being "incorporated" as part of the polymeric backbone of the aliphatic condensation polymer is meant that the cyclic ester ring opens and becomes covalently bound to the polymeric backbone.
  • this process at least involves the ring opened residue being covalently bound to a terminal end of the polymeric backbone, possibly followed by inter and/or intra polymer chain rearrangement of the ring opened residue such that it becomes located at a non-terminal position within the polymeric backbone (e.g. through a transesterification process).
  • the ring opened form of the cyclic ester may initially attach to a terminal section of the aliphatic condensation polymer, it may nevertheless rearrange its position within the polymer backbone through a transesterification process.
  • an aliphatic condensation polymer modified in accordance with the invention using a cyclic ester of general formula (VIII) may comprise within its polymeric backbone the ring opened residue of the cyclic ester as illustrated below in Scheme 1.
  • the modified condensation polymer will of course generally comprise within its polymeric backbone a number of such ring opened residues.
  • Scheme 1 An illustration of an aliphatic condensation polymer modified in accordance with the invention using a cyclic ester of general formula (VIII), where A and B represent the remainder of the condensation polymer.
  • VIII cyclic ester of general formula (VIII)
  • a and B represent the remainder of the condensation polymer.
  • the R group of the ⁇ -oxy carbonyl moiety of general formula (I) is believed to modify the properties of the condensation polymer.
  • polylactic acid modified in accordance with the invention has been shown to exhibit improved flexibility.
  • Other pendant moieties derived from the cyclic ester, such as R 1 shown above in Scheme 1, may also modify the properties of the condensation polymer.
  • a condensation catalyst may also be employed in order to enhance the melt reaction between the aliphatic condensation polymer and the cyclic ester.
  • Typical condensation catalysts include Lewis acids such as antimony trioxide, titanium oxide and dibutyl tindilaurate.
  • Melt mixing of the aliphatic condensation polymer and the cyclic ester may also be conducted in the presence of one or more additives such as fillers, pigments, stabilisers, blowing agents, nucleating agents, and chain coupling and/or branching agents.
  • additives such as fillers, pigments, stabilisers, blowing agents, nucleating agents, and chain coupling and/or branching agents.
  • Chain coupling and/or branching agents may be used in accordance with the invention to promote an increase in the molecular weight of and/or chain branching in the aliphatic condensation polymer.
  • Such agents include polyfunctional acid anhydrides, epoxy compounds, oxazoline derivatives, oxazolinone derivatives, lactams and related species.
  • Suitable chain coupling and/or branching agents include one or more of the following:
  • Polyepoxides such as bis(3,4-epoxycyclohexylmethyl) adipate; N,N-diglycidyl benzamide (and related diepoxies); N,N-diglycidyl aniline and derivatives; N,N-diglycidylhydantoin, uracil, barbituric acid or isocyamiric acid derivatives; N,N-diglycidyl diimides; N,N- diglycidyl imidazolones; epoxy novolaks; phenyl glycidyl ether; diethyleneglycol diglycidyl ether; Epikote 815 (diglycidyl ether of bisphenol A-epichlorohydrin oligomer).
  • Polyoxazolines/Polyoxazolones such as 2,2-bis(2-oxazoline); 1,3-phenylene bis(2- oxazoline-2), l,2-bis(2-oxazolinyl-2)ethane; 2-phenyl-l,3-oxazoline; 2,2'-bis(5,6-dihydro- 4H-l,3-oxazoline); N,N'-hexamethylenebis (carbamoyl-2-oxazoline; bis[5(4H)- oxazolone); bis(4H-3,lbenzoxazin-4-one); 2,2'-bis(H-3,l-benzozin-4-one).
  • Polyfunctional acid anhydrides such as pyromellitic dianhydride, benzophenonetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic dianhydride, diphenyl sulphone tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3- methyl-3-cyclohexene-l ,2-dicarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride, bisphenol-A bisether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,3,6,7- naphthalenetetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)sulphone dianhydride, 1,2,5,6-naphthal
  • Suitable polyfunctional acid anhydrides include pyromellitic dianhydride, ⁇ , 2,3, A- cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride. Most preferably the polyfunctional acid anhydride is pyromellitic dianhydride.
  • Polyacyllactams such as N,N'-terephthaloylbis(caprolactarn) and N,N'- terephthaloylbis(laurolactam) may also be employed.
  • the polymer composition resulting from the methods of the invention may also be subjected to a subsequent solid state condensation polymerisation process. This further processing step can assist with building the molecular weight of the modified aliphatic condensation polymer and can advantageously be conducted using conventional solid state condensation polymerisation techniques and equipment.
  • the cyclic ester When performing the methods of the invention, it may be convenient to provide the cyclic ester, optionally together with any other additives that are to be used, in the form of a composition that can be used for producing the modified aliphatic condensation polymer.
  • This composition may be provided in the form of a physical blend of the respective components and/or in the form a melt mixed product.
  • the invention therefore also provides a composition for modifying an aliphatic condensation polymer, the composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I), and/or a product formed by melt mixing a composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ⁇ -oxy carbonyl moiety of general formula (I).
  • the carrier polymer may in fact be the aliphatic condensation polymer that is to be modified in accordance with the invention.
  • the composition may simplistically be a physical blend of the cyclic ester and the polymer, and the method of the invention is preformed by melt mixing that composition.
  • cyclic ester in the form of a masterbatch or concentrate which can be subsequently melt mixed with an aliphatic condensation polymer that is to be modified in accordance with the invention.
  • masterbatch or “concentrate” (to be used synonymously herein) has the common meaning as would be understood by one skilled in the art. With particular reference to the present invention, these terms are therefore intended to mean a composition comprising the cyclic ester and one or more carrier polymers, which composition is to be subsequently let down in an aliphatic condensation polymer in order to perform the methods of the invention.
  • the masterbatch may be formed by melt mixing the cyclic ester with a carrier polymer that is considered appropriate under the circumstance to be melt mixed with the aliphatic condensation polymer that is to be modified.
  • the carrier polymer may be an aliphatic condensation polymer, for example an aliphatic condensation polymer of the same type as the one that is to be modified.
  • the carrier polymer is an aliphatic condensation polymer
  • the process of making the masterbatch in effect employs the method of the invention.
  • the intention is for the masterbatch to be employed in performing the methods of the invention, hi other words, it is the intention that the masterbatch will comprise unreacted cyclic ester that can be subsequently melt mixed with an aliphatic condensation polymer so as to perform the methods of the invention.
  • a masterbatch formed by melt mixing the cyclic ester with an aliphatic condensation polymer may itself comprise aliphatic condensation polymer that has been modified in accordance with the invention. Melt mixing this modified aliphatic condensation polymer per se with further aliphatic condensation polymer (as will be the case when the masterbatch is melt mixed with an aliphatic condensation polymer) can itself result in the further aliphatic condensation polymer being modified as described herein (e.g. in the case of polyesters, through transesterification reactions).
  • Aliphatic condensation polymers that may be used as a carrier polymer in the compositions of the invention include those described herein.
  • Preparing a masterbatch by melt mixing the cyclic ester with an aliphatic condensation polymer and then subsequently melt mixing the masterbatch with an aliphatic condensation polymer is believed to provide a more efficient and effective means of incorporating the ring opended residues as part of the polymeric backbone of the aliphatic condensation polymer.
  • melt mixing of the cyclic ester and the aliphatic condensation polymers will be conducted at a temperature ranging from about 120°C to about 240°C.
  • the properties of the aliphatic condensation polymer is modified in at least some way, there is no particular limitation on the amount of cyclic ester that is to be melt mixed with the aliphatic condensation polymer.
  • the cyclic ester will generally be used in an amount ranging from about 5 wt.% to about 35 wt.%, preferably 5 wt.% to about 20 wt.%, relative to the mass of the cyclic ester and the aliphatic condensation polymer.
  • the cyclic ester will generally be used in an amount ranging from about 30 wt.% to about 80 wt.%, relative to the total mass of the cyclic ester and the one or more carrier polymers.
  • Cyclic esters used in accordance with the methods of the invention can impart to the resulting modified aliphatic condensation polymers properties such as improved flexibility, an alteration in its hardness (either decreased through the incorporation of softer segments provided by the R group, or increased through crosslinking induced from reaction of functional groups within or pendant from the R group), an alteration in its surface properties (e.g. hydrophobicity provided by the R group), altered degradation rates (either decreased through making the polymer overall more hydrophobic (e.g.
  • hydrophobicity provided by the R group and so less prone to hydrolytic attack, or increased through the introduction via the R group of hydrolytically liable groups to a relatively stable polymer), an alteration in its stiffness (either decreased through the R group breaking up crystallininty, or increased through crosslinking induced from reaction of functional groups within or pendant from the R group), and improved melt viscosity or melt strength resulting directly from the presence of the R group, or through long chain branching induced from reaction of functional groups within or pendant from the R group and the base polymer.
  • an aliphatic condensation polymer may also be converted into a thermoset polymer via reaction of functional groups within or pendant from the R group (e.g. oxidative crosslinking of a coating product produced from the modified polymer, or crosslinking reactions where the modified condensation polymer is included in the formulation of a thermoset resin such as a unsaturated polyester, vinyl ester resin, epoxy resin etc).
  • a thermoset resin such as a unsaturated polyester, vinyl ester resin, epoxy resin etc.
  • the stability (e.g. UV) or colour fastness of a modified aliphatic condensation polymer prepared in accordance with the invention may also be improved by tethering an appropriate moiety to the R group (e.g. moieties such as stabilises (e.g. hindered phenols and hindered amine light stabilisers), alkoxy amines, dyes, and bioactive materials).
  • an appropriate moiety to the R group e.g. moieties such as stabilises (e.g. hindered phenols and hindered amine light stabilisers), alkoxy amines, dyes, and bioactive materials).
  • modified condensation polymers of this invention can advantageously be utilised in products ranging from: films for packaging applications, injection moulded articles, blow moulded containers, sheet products, thermoformed items, coatings, adhesives, fibres, scaffolds for medical applications including tissue repair and drug delivery.
  • Proton NMR spectra were obtained on Bruker AV400 and Bruker AV200 spectrometer, operating at 400 MHz and 200 MHz. All spectra were obtained at 23 0 C unless specified. Chemical shifts are reported in parts per million (ppm) on the ⁇ scale and relative to the chloroform peak at 7.26 ppm ( 1 H) or the TMS peak at 0.00 ppm ( 1 H). Oven dried glassware was used in all reactions carried out under an inert atmosphere (either dry nitrogen or argon). All starting materials and reagents were obtained commercially unless otherwise stated.
  • Removal of solvents "under reduced pressure” refers to the process of bulk solvent removal by rotary evaporation (low vacuum pump) followed by application of high vacuum pump (oil pump) for a minimum of 30 min.
  • Analytical thin layer chromatography (TLC) was performed on plastic-backed Merck Kieselgel KGoOF 254 silica plates and visualised using short wave ultraviolet light, potassium permanganate or phosphomolybdate dip. Flash chromatography was performed using 230-400 mesh Merck Silica Gel 60 following established guidelines under positive pressure. Tetrahydrofuran and dichloromethane were obtained from a solvent dispensing system under an inert atmosphere. All other reagents and solvents were used as purchased.
  • the combined organic layers were washed with saturated aqueous ammonium chloride solution (1 x, 1 A volume of the organic layer), water (1 x, 1 A volume of the organic layer) and brine (1 x, 1 A volume of the organic layer) and dried over sodium sulphate. After filtration, the organic solvent was removed under reduced pressure leaving the crude product. If necessary, the crude product was recrystallised from acetone.
  • the reaction mixture was diluted with water (200 ml), acidified with IN aqueous hydrochloric acid (pH 2) and extracted with diethylether 3 x 100 ml). The combined organic layers were washed with brine (1 x 100 ml) and dried over sodium sulphate. After filtration, the organic solvent was removed under reduced pressure leaving the crude product. The crude product was recrystallised from hexane (4.6 g, 15.4 mmol, 87 %).
  • the reaction mixture was diluted with water (200 ml), acidified with IN aqueous hydrochloric acid (pH 2) and extracted with diethylether 3 x 100 ml). The combined organic layers were washed with brine (1 x 100 ml) and dried over sodium sulphate. After filtration, the organic solvent was removed under reduced pressure leaving the crude product. The crude product was recrystallised from hexane (2.87 g, 14.3 mmol, 81 %).
  • the resulting crude product was dissolved in dry acetone (200 ml), triethylamine (1.36 g, 13.4 mmol) was added and the reaction mixture was heated to reflux for 12 h. After that the solvent was removed under reduced pressure, the crude product was redissolved in diethyl ether (100 ml), successively extracted with 0.5 M aqueous HCl solution (100 ml) and saturated aqueous NaHCO 3 solution and dried over MgSO 4 . The crude product was purified via column chromatography (0.80 g, 2.24 mmol, 67 %).
  • PLA Polylactic acid - Natureworks 305 ID, supplied by Cargill, USA
  • Nylon 11 Rilsan BESNO TL (Check?), supplied by Arkema, France
  • Scheme 2 Schematic setup of the Prism twin screw extruder use to melt modify the polymers with the lactone.
  • the lactone monomer was dried under vacuum at 80C with stirring.
  • the lactone was mixed with 0.1 wt% of the liquid catalyst and then charged into the heated barrel (80C) of an ISCO 500D syringe pump fitted with a heated line to dispense the lactone into the barrel of the twin screw extruder.
  • the gravimetric output of the ISCO syringe pump was calibrated at a number of relevant volumetric throughput rates prior to connecting to the extruder.
  • the polymer was dried in a small scale hopper drier using dry air at temperatures according to the manufacturer's recommendations. All samples were dried to ⁇ lOOppm water, as measured using an Arizona Instruments moisture analyser.
  • the dried polymer was fed to the extruder via a Barrell single screw volumetric feeder.
  • the feeder and extruder hopper were flushed with dry air to prevent moisture ingress.
  • the gravimetric output of the feeder and extruder were monitored by collecting samples before and after collecting samples.
  • the extruder was fitted with a lmm rod die and operated at a throughput of rate of approximately 25g/hour. The exact throughput rate was determined for each sample.
  • the extraded samples which were subsequently melt pressed were collected in sample jars purged with dry nitrogen. Melt pressing was carried in an IHMS melt press ( 250 by 250mm plattern) fitted with brass plates through water could be passed to cool the sample after pressing. Samples were pressed between Teflon sheets. A 150 by 150 by 0.150 mm shim plate was used for the melt pressing.
  • the lactone monomer and catalyst was dissolved in the minimum quantity of solvent (hexane). The solution was coated onto cryo ground polymer powder. The excess solvent was removed by rotovap and vacuum oven.
  • the lactone coated polymer was dried in a small scale hopper drier using dry air at temperatures according to the manufacturer's recommendations. All samples were dried to ⁇ lOOppm water, as measured using an Arizona Instruments moisture analyser.
  • the dried lactone coated polymer was fed to the extruder via a Barrell single screw volumetric feeder.
  • the feeder and extruder hopper were flushed with dry air to prevent moisture ingress.
  • the gravimetric output of the feeder and extruder were monitored by collecting samples before and after collecting samples.
  • the extruder was fitted with a lmm rod die and operated at a throughput of rate of approximately 25g/hour. The exact throughput rate was determined for each sample.
  • the extruded samples which were subsequently melt pressed were collected in sample jars purged with dry nitrogen. Melt pressing was carried in an IHMS melt press ( 250 by 250mm plattern) fitted with brass plates through water could be passed to cool the sample after pressing. Samples were pressed between Teflon sheets. A 150 by 150 by 0.150 mm shim plate was used for the melt pressing.
  • Polymers were dried using the same methodology as was used for the extrusion samples.
  • the lactone samples were vacuum dried prior to use.
  • the 25ml round bottom flasks used for the experiments were cleaned, fitted with large magnetic spinbars and dried in an oven set at 80C. Upon removal from the oven the flasks were stoppered and allowed to cool. Upon opening the flasks to add the reagents, the flasks were flushed with dry nitrogen.
  • the flasks were then placed in a silicone oil bath on top of a magnetic stirrer hotplate.
  • the oil temperature was controlled to the desired temperature (210C for PLA, 240C for Nylon 11) and monitored via a calibrated thermometer.
  • Polymers were dried using the same methodology as was used for the extrusion samples.
  • the lactone samples were vacuum dried prior to use.
  • the 100ml round bottom flasks used for the experiments were cleaned and dried in an oven set at 80C. Upon removal from the oven the flasks were stoppered and allowed to cool. Upon opening the flasks to add the reagents, the flasks were flushed with dry nitrogen. The flasks were then fitted with metal stirrers having two blades. The stirrers were connected to overhead drive motors. The stirrers were held in place by a glass adapter fitted with a Teflon bearing fitted with a rubber seal. The glass adaptor was also fitted with a water cooled Leibig condenser and a separate nitrogen inlet to prevent moisture ingress.
  • the flasks fitted with the adaptors, condensers and stirrers were then placed in a silicone oil bath on top of a magnetic stirrer hotplate.
  • the oil temperature was controlled to the desired temperature ( 200C for PLA, 250C for Nylon 11) and monitored via a calibrated thermometer.
  • stirrers and condensers were removed and samples were poured from the flasks under a blanket of dry nitrogen. The samples were then allowed to cool. For melt pressing samples were reheated in a vacuum oven, sub-samples were removed for analysis from the flasks and were melt pressed using the same procedure as was used for the extrusion samples.
  • Polymer samples were characterised by a number of techniques as described below.
  • the thermal behaviour of the samples was determined by differential scanning calorimetry ( DSC) using a Mettler Toloedo DSC 85 Ie DSC system. Samples were weighed into 40ul pans and lids were crimped onto the pans. A hole was then made in the lids with a 20 gauge needle to prevent pressurisation. All scans were carried out at a scanning rate of 10 degrees Celsius (C) per minute. Scan were typically as follows; (i) heating from 20 to either 180C (polyesters) or 220C (polyamides); (ii) then the pans were held at the elevated temperature for 3 minutes;(iii) then cooled at 10 C/min.
  • a — mole% modifier' calculated as moles of modifier fatty acid.
  • the moles of alpha hydroxyl fatty acid introduced is a multiple of the size of the lactone.
  • For di-lactones 2 moles of acid are introduced per mole of lactone.
  • the modified material can be used as a masterbatch
  • a amount of the modified polymer (Example 15) was dried and was melt mixed with as an equal wt:wt basis with PLA pellets using the method RBF-2.
  • the signal of the hydrogen between carbonyl and alcohol functionality can be used to determine the level of incorporation of symmetric dilactones into the nylon chain. Incorporation of a modifying unit causes a shift in this signal.
  • the signal of the PLA methyl group can be used to determine the level of incorporation of symmetric dilactones into the PLA chain. Incorporation of a modifying unit causes a shift in this signal.
  • # DSC data taken from first heat cycle of sample a - PLA and Nylon 11 controls are for samples which have been melt mixed under the same conditions. Times represent melt mixing times, b - Major peak in bold TENSILE

Abstract

The present invention relates to a method of preparing a polymer composition, the method comprising melt mixing an aliphatic condensation polymer with a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of a general formula (I) where R is an optionally substituted aliphatic hydrocarbon having 3 or more carbon atoms.

Description

CONDENSATION POLYMERS
FIELD OF THE INVENTION
The present invention relates in general to condensation polymers. In particular, the invention relates to aliphatic condensation polymers having modified properties
BACKGROUND OF THE INVENTION
Condensation polymers such as polyesters and polyamides may be prepared with a diverse array of physical and chemical properties. For example, condensation polymers may vary widely in their stiffness, hardness, elasticity, tensile strength, density, and may or may not be susceptible to biodegradation.
Such diverse properties lend this class of polymer utility in many and varied applications including food packaging, building materials, medical implants, to name but a few.
As a subset of condensation polymers, aliphatic condensation polymers present their own unique physical and chemical properties. For example, aliphatic polyesters are known to exhibit good biodegradability. However, relative to their non-aliphatic counterparts and other commercial polymers (e.g. polyvinyl chloride and polypropylene), aliphatic condensation polymers can lack the physical and/or chemical properties required for use in certain applications. For example, despite exhibiting good biodegradability, polylactic acid has relatively poor flexibility and its use in film based applications (e.g. as a packaging material) is limited.
A number of techniques for improving the physical and/or chemical properties of aliphatic condensation polymers have been developed. For example, specialty monomers that can influence the physical and/or chemical properties of the polymer may be used in conjunction with the conventional monomers during the condensation polymerisation manufacturing process. However, deriving new and improved properties of condensation polymers in this way necessarily requires the use of rather specialised condensation polymerisation equipment.
An opportunity therefore remains to develop alternative methodology for preparing aliphatic condensation polymers with new and/or improved properties.
SUMMARY OF THE INVENTION
The present invention provides a method of preparing a polymer composition, the method comprising melt mixing an aliphatic condensation polymer with a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I):
Figure imgf000003_0001
where R is an optionally substituted aliphatic hydrocarbon having 3 or more carbon atoms.
By melt mixing the cyclic ester of general formula (I) with a preformed aliphatic condensation polymer, it has been found that the polymer backbone of the condensation polymer can be modified so as to incorporate the α-oxy carbonyl moiety. Furthermore, this process has been found to occur without significant loss of molecular weight of the condensation polymer, thereby minimising if not avoiding all together the need for any subsequent processing to build the molecular weight of the modified polymer.
The resulting modified condensation polymer includes as part its polymeric backbone the α-oxy carbonyl moiety of a general formula (T). The presence of the moiety as part of the polymer backbone is believed to impart new and/or improved properties to the modified condensation polymer.
Accordingly, the present invention further provides a method for modifying an aliphatic condensation polymer, the method comprising melt mixing the condensation polymer with a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an ce-oxy carbonyl moiety of general formula (I).
The methods of the invention can advantageously be performed using conventional melt mixing equipment known in the art. Generally, the methods will be performed by introducing the cyclic ester and the condensation polymer individually or collectively into the appropriate melt mixing equipment. For example, the cyclic ester might be introduced to condensation polymer already in a molten state, or a mixture of the cyclic ester and the condensation polymer may be subjected to melt mixing.
The cyclic ester might also be provided in the form of a composition such as a masterbatch or concentrate which is subsequently let down into an aliphatic condensation polymer to be modified. The composition will generally comprise the cyclic ester and one or more polymers (commonly referred to as a carrier polymer(s)). The carrier polymer may be the same or different to the condensation polymer that is to be modified. In one embodiment, the carrier polymer(s) is an aliphatic condensation polymer. The composition may be a physical blend of the cyclic ester and one or more carrier polymers, and/or may itself be prepared by melt mixing the cyclic ester with one or more carrier polymers.
The present invention therefore also provides a composition for modifying an aliphatic condensation polymer, the composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I), and/or a product formed by melt mixing a composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I). In one embodiment, the polymer composition comprises an aliphatic condensation polymer and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I) and/or a product formed by melt mixing a composition comprising an aliphatic condensation polymer and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I).
Aliphatic condensation polymers modified in accordance with the invention have been found to exhibit new and/or improved properties such as improved flexibility relative to the condensation polymer prior to being modified.
The cyclic esters used in accordance with the invention can advantageously be prepared using hydroxycarboxylic acids, a renewable resource that can be derived from plants and animals.
Further aspects of the invention are described below.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the expression "condensation polymer" is intended to mean a polymer that has been formed via a condensation or step-wise polymerisation reaction. Examples of condensation polymers include polyesters, polyamide and copolymers thereof. In one embodiment of the invention, the condensation polymers used are polyesters, polyamides, and copolymers thereof.
Condensation polymers used in accordance with the invention are "aliphatic condensation polymers". By "aliphatic" condensation polymers is meant that the polymer backbone does not incorporate an aromatic moiety. Thus, polyethylene terephthalate (i.e. PET) is not an aliphatic polyester.
By the expression "polymer backbone" is meant the main structure of the polymer on to which substituents may be attached. The main structure of the polymer may be linear or branched.
The condensation polymers may also be acyclic (i.e. where the polymer backbone does not incorporate a cyclic moiety). Although the polymer backbone of the aliphatic condensation polymers will not incorporate an aromatic moiety (and possibly not a cyclic moiety), an aromatic or cyclic moiety may nonetheless be present in a position that is pendant from the polymer backbone. However, the aliphatic condensation polymers used in accordance with the invention will not generally comprise a pendant aromatic or cyclic moiety.
Aliphatic polyesters that may be used in the invention include homo- and copolymers of ρoly(hydroxyalkanoates) and homo- and copolymers of those aliphatic polyesters derived from the reaction product of one or more alkyldiols with one or more alkyldicarboxylic acids (or acyl derivatives). Miscible and immiscible blends of aliphatic polyesters may also be used.
One class of aliphatic polyester includes poly(hydroxyalkanoates) derived by condensation or ring-opening polymerization of hydroxycarboxylic acids, or derivatives thereof. Suitable poly(hydroxyalkanoates) may be represented by the formula H(O — Ra — C(O) — )nOH, where Ra is an alkylene moiety that may be linear or branched and n is a number from 1 to 20, preferably 1 to 12. Ra may further comprise one or more caternary (i.e. in chain) ether oxygen atoms. Generally the Ra group of the hydroxycarboxylic acids is such that the pendant hydroxyl group is a primary or secondary hydroxyl group.
Useful poly(hydroxyalkanoates) include, for example, homo- and copolymers of poly(3- hydroxybutyrate), poly(4-hydroxybutyrate), poly(3-hydroxyvalerate), poly(lactic acid) (also known as polylactide), poly(3-hydroxypropanoate), poly(4-hydropcntanoate), ρoly(3- hydroxypentanoate), poly(3-hydroxyhexanoate), poly(3-hydroxyheptanoate), poly(3- hydroxyoctanoate), polydioxanone, and polycaprolactone, polyglycolic acid (also known as polyglycolide). Copolymers of two or more of the above hydroxycarboxylic acids may also be used, for example, to provide for poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polyClactate-co-S-hydroxypropanoate) and poly^lycolide-co-p-dioxanone). Blends of two or more of the poly(hydroxyalkanoates) may also be used.
A further class of aliphatic polyester includes those aliphatic polyesters derived from the reaction product of one or more alkyldiols with one or more alkyldicarboxylic acids (or acyl derivatives). Such polyesters may have the general formula (II):
Figure imgf000007_0001
(II)
where Rb and Rc each independently represent an alkylene moiety that may be linear or branched having from 1 to 20, preferably 1 to 12 carbon atoms, and p is a number such that the ester is polymeric, and is preferably a number such that the molecular weight of the aliphatic polyester is 10,000 to 300,000, more preferably from about 30,000 to 200,000. Each m and n is independently 0 or 1. Rb and Rc may further comprise one or more caternary (i.e. in chain) ether oxygen atoms.
Examples of such aliphatic polyesters include those homo- and copolymers derived from (a) one or more of the following diacids (or derivative thereof): succinic acid, adipic acid, 1,12 dicarboxydodecane, fumaric acid, and maleic acid and (b) one of more of the following diols: ethylene glycol, polyethylene glycol, 1,2-propane diol, 1,3-propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and polypropylene glycol, and (c) optionally a small amount, e.g. 0.5-7.0 mole % of a polyol with a functionality greater than two such as glycerol, or pentaerythritol.
Such aliphatic polyesters may include polybutylenesuccinate homopolymer, polybutylene adipate homopolmer, polybutyleneadipate-succinate copolymer, polyethylenesuccinate- adipate copolymer, polyethylene adipate homopolymer. Common commercially available aliphatic polyesters include polylactide, polyglycolide, polylactide-co-glycolide, poly(L-lactide-co-trimethylene carbonate), poly(dioxanone), poly(butylene succinate), and poly(butylene adipate).
Blends of two or more aliphatic polyesters may also be used in accordance with the invention.
Aliphatic polyamides that may be used in the invention include those characterised by the presence of recurring carbonamide groups that form part of the polymer backbone and which are separated from one another by at least two aliphatic carbon atoms. Suitable aliphatic polyamides therefore include those having recurring units represented by general formulae (III) or (IV):
O O
-N- -Rd -N- Re
H H (III)
Figure imgf000008_0001
(IV)
or a combination thereof, in which Rd and Re are the same or different and are each independently alkylene groups of at least two carbon atoms, for example alkylene having about two to about 20 carbon atoms, preferably alkylene having about two to about 12 carbon atoms.
Examples of such polyamides are those formed by the reaction of one or more alkyldiarnines and one or more alkyldicarboxylic acids and include poly(tetramethylene adipamide) (nylon 4,6); pory(hexamethylene adipamide) (nylon 6,6); poly(hexamethylene azelamide) (nylon 6,9); poly(hexamethylene sebacamide) (nylon 6,10); poly(heptamethylene pimelamide) (nylon 7,7); poly(octamethylene suberamide) (nylon 8,8); pory(nonamethylene azelamide) (nylon 9,9); poly(decamethylene azelamide) (nylon 10,9); and the like.
Examples of polyamides are also those formed by polymerization of alkyl amino acids and derivatives thereof (e.g. lactams) and include poly(4-aminobutyric acid) (nylon 4); poly(6- aminohexanoic acid) (nylon 6); poly(7-amino-heptanoic acid) (nylon 7); poly(8- aminoocatanoic acid) (nylon 8); poly(9-aminononanoic acid) (nylon 9); poly(10- aminodecanoic acid) (nylon 10); poly(ll-aminoundecanoic acid) (nylon 11); poly(12- aminododecanoic acid) (nylon 12); and the like.
Blends of two or more aliphatic polyamides may also be used in accordance with the invention.
As used herein, a the expression "cyclic ester" is intended to mean a cyclic molecule having at least one ring (or cycle) within its molecular structure that contains an ester moiety that forms part of that cycle. In accordance with the invention, the cyclic ester has at least two ester moieties that form part of its cycle. Those skilled in the art will appreciate that such cyclic esters are commonly referred to as macrocyclic oligoesters.
The cyclic esters used in accordance with the invention comprise as part of their cycle an α-oxy carbonyl moiety of general formula (I):
Figure imgf000009_0001
(I) where R is an optionally substituted aliphatic hydrocarbon having three or more carbon atoms.
R in general formula (I) is an optionally substituted aliphatic hydrocarbon having three or more carbon atoms. By "aliphatic" hydrocarbon is meant a non-aromatic hydrocarbon. The hydrocarbon group R may also be an acyclic hydrocarbon (i.e. a non-cyclic hydrocarbon). The hydrocarbon group R may be a linear or branched alkyl, alkenyl, or alkynyl group.
The hydrocarbon group R may be saturated or unsaturated. Where the hydrocarbon group R is unsaturated, it may be mono- or poly-unsaturated, and include both cis- and trans- isomers. The hydrocarbon R will generally have 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 6 to 20 carbon atoms.
The hydrocarbon R may be substituted, for example with a hetero atom containing moiety and/or an aromatic or cyclic moiety. In some embodiments the R group is not substituted.
Where the R group in general formula (I) is an unsaturated aliphatic hydrocarbon group, or an aliphatic hydrocarbon group substituted with one or more optional substituents as herein defined that present a reactive functional group, the modified condensation polymers in accordance with the invention can advantageously undergo reaction through the reactive functional groups within or substituted on the hydrocarbon R. For example, where the hydrocarbon group R is unsaturated, the unsaturated bonds may take part in crosslinking reactions (i.e. oxidative crosslinking similar to that which occurs in alkyd paints, or free radical mediated reactions), and free radical mediated grafting reactions. Crosslinking and grafting reactions may also be conducted through reactive functional group substituents on the hydrocarbon group R.
Providing the hydrocarbon group R with one or more reactive functional groups can advantageously enable organic or inorganic moieties to be tethered to the polymer backbone through reaction of the moieties with such groups. The organic or inorganic moieties may be conveniently tethered to the R group of the cyclic ester prior to it being melt mixed with the aliphatic condensation polymer, or tethered to the R group after the cyclic ester has been melt mixed with the aliphatic condensation polymer.
In one embodiment, the R group of general formula (I) is an aliphatic hydrocarbon comprising conjugated double and/or triple bonds. Preferably, such conjugation is in the form of an yne-yne, ene-ene, yne-yne-yne, yne-yne-ene-, ene-yne-yne or yne-ene-yne moiety.
As used herein, the term "alkyl", used either alone or in compound words denotes straight chain, branched or cyclic alkyl, for example C1-40 alkyl, or C1-20 or C1-10. Examples of straight chain and branched alkyl include methyl, ethyl, π-propyl, isopropyl, ra-butyl, sec- butyl, t-butyl, n-pentyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, hexyl, 4-methylpentyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3- dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2- trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3- dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4- dimethyl-pentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6- methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-, 3-, 4-, 5-, 6- or 7- methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheρtyl, 1-, 2- or 3-ρroρylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl, 1-, 2-, 3-, A-, 5-, 6-, 7-, 8- or 9-methyldecyl, X-, 2-, 3-, A-, 5-, 6- or 7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, A-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, A-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-, A-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1-2-pentylheptyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonoadecyl, eicosyl and the like. Examples of cyclic alkyl include mono- or polycyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Where an alkyl group is referred to generally as "propyl", butyl" etc, it will be understood that this can refer to any of straight, branched and cyclic isomers where appropriate. An alkyl group may be optionally substituted by one or more optional substituents as herein defined.
As used herein, term "alkenyl" denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon to carbon double bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined, for example C2-40 alkenyl, or C2-20 or C2-10. Thus, alkenyl is intended to include propenyl, butylenyl, pentenyl, hexaenyl, heptaenyl, octaenyl, nonaenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nondecenyl, eicosenyl hydrocarbon groups with one or more carbon to carbon double bonds. Examples of alkenyl include vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1 -pentenyl, cyclopentenyl, 1-methyl- cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl, 1,4- pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloheptatrienyl and 1,3,5,7- cyclooctatetraenyl. An alkenyl group may be optionally substituted by one or more optional substituents as herein defined.
As used herein the term "alkynyl" denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon-carbon triple bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined, for example, C2-40 alkenyl, or C2-20 or C2-10. Thus, alkynyl is intended to include propynyl, butylynyl, pentynyl, hexaynyl, heptaynyl, octaynyl, nonaynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nondecynyl, eicosynyl hydrocarbon groups with one or more carbon to carbon triple bonds. Examples of alkynyl include ethynyl, 1 -propynyl, 2-propynyl, and butynyl isomers, and pentynyl isomers. An alkynyl group may be optionally substituted by one or more optional substituents as herein defined. An alkenyl group may comprise a carbon to carbon triple bond and an alkynyl group may comprise a carbon to carbon double bond (i.e. so called ene-yne or yne-ene groups).
As used herein, the term "aryl" (or "carboaryl)" denotes any of single, polynuclear, conjugated and fused residues of aromatic hydrocarbon ring systems. Examples of aryl include phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl, fluorenyl, pyrenyl, idenyl, azulenyl, chrysenyl. Preferred aryl include phenyl and naphthyl. An aryl group may be optionally substituted by one or more optional substituents as herein defined.
As used herein, the terms "alkylene", "alkenylene", and "arylene" are intended to denote the divalent forms of "alkyl", "alkenyl", and "aryl", respectively, as herein defined.
hi this specification "optionally substituted" is taken to mean that a group may or may not be substituted or fused (so as to form a condensed polycyclic group) with one, two, three or more of organic and inorganic groups (i.e. the optional substituent) including those selected from: alkyl, alkenyl, alkynyl, carbocyclyl, aryl, heterocyclyl, heteroaryl, acyl, aralkyl, alkaryl, alkheterocyclyl, alkheteroaryl, alkcarbocyclyl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, halocarbocyclyl, haloheterocyclyl, haloheteroaryl, haloacyl, haloaryalkyl, hydroxy, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, hydroxycarbocyclyl, hydroxyaryl, hydroxyheterocyclyl, hydroxyheteroaryl, hydroxyacyl, hydroxyaralkyl, alkoxyalkyl, alkoxyalkenyl, alkoxyalkynyl, alkoxycarbocyclyl, alkoxyaryl, alkoxyheterocyclyl, alkoxyheteroaryl, alkoxyacyl, alkoxyaralkyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, carbocyclyloxy, aralkyloxy, heteroaryloxy, heterocyclyloxy, acyloxy, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloaryloxy, halocarbocyclyloxy, haloaralkyloxy, haloheteroaryloxy, haloheterocyclyloxy, haloacyloxy, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, nitroheteroayl, nitrocarbocyclyl, nitroacyl, nitroaralkyl, amino (NH2), alkylamino, dialkylamino, alkenylamino, alkynylamino, arylamino, diarylamino, aralkylamino, diaralkylamino, acylamino, diacylamino, heterocyclamino, heteroarylamino, carboxy, carboxyester, amido, alkylsulphonyloxy, arylsulphenyloxy, alkylsulphenyl, arylsulphenyl, thio, alkylthio, alkenylthio, alkynylthio, arylthio, aralkylthio, carbocyclylthio, heterocyclylthio, heteroarylthio, acylthio, sulfoxide, sulfonyl, sulfonamide, aminoalkyl, aminoalkenyl, aminoalkynyl, aminocarbocyclyl, aminoaryl, aminoheterocyclyl, aminoheteroaryl, aminoacyl, aminoaralkyl, thioalkyl, thioalkenyl, thioalkynyl, thiocarbocyclyl, thioaryl, thioheterocyclyl, thioheteroaryl, thioacyl, thioaralkyl, carboxyalkyl, carboxyalkenyl, carboxyalkynyl, carboxycarbocyclyl, carboxyaryl, carboxyheterocyclyl, carboxyheteroaryl, carboxyacyl, carboxyaralkyl, carboxyesteralkyl, carboxyesteralkenyl, carboxyesteralkynyl, carboxyestercarbocyclyl, carboxyesteraryl, carboxyesterheterocyclyl, carboxyesterheteroaryl, carboxyesteracyl, carboxyesteraralkyl, amidoalkyl, amidoalkenyl, amidoalkynyl, amidocarbocyclyl, amidoaryl, amidoheterocyclyl, amidoheteroaryl, amidoacyl, amidoaralkyl, formylalkyl, formylalkenyl, formylalkynyl, formylcarbocyclyl, formylaryl, formylheterocyclyl, formylheteroaryl, formylacyl, formylaralkyl, acylalkyl, acylalkenyl, acylalkynyl, acylcarbocyclyl, acylaryl, acylheterocyclyl, acylheteroaryl, acylacyl, acylaralkyl, sulfoxidealkyl, sulfoxidealkenyl, sulfoxidealkynyl, sulfoxidecarbocyclyl, sulfoxidearyl, sulfoxideheterocyclyl, sulfoxideheteroaryl, sulfoxideacyl, sulfoxidearalkyl, sulfonylalkyl, sulfonylalkenyl, sulfonylalkynyl, sulfonylcarbocyclyl, sulfonylaryl, sulfonylheterocyclyl, sulfonylheteroaryl, sulfonylacyl, sulfonylaralkyl, sulfonamidoalkyl, sulfonamidoalkenyl, sulfonamidoalkynyl, sulfonamidocarbocyclyl, sulfonamidoaryl, sulfonamidoheterocyclyl, sulfonamidoheteroaryl, sulfonamidoacyl, sulfonamidoaralkyl, nitroalkyl, nitroalkenyl, nitroalkynyl, nitrocarbocyclyl, nitroaryl, nitroheterocyclyl, nitroheteroaryl, nitroacyl, nitroaralkyl, cyano, sulfate and phosphate groups.
In some embodiments, it may be desirable that a group is optionally substituted with a reactive functional group or moiety. Examples of such reactive functional groups or moieties include epoxy, anhydride, cyclic ester (e.g. lactone or higher cyclic oligoester), cyclic amide (e.g. lactam or higher cyclic oligoamide), oxazoline and carbodimide.
In some embodiments, it may be desirable that a group is optionally substituted with a polymer chain. An example of such a polymer chain includes a polyether chain. Preferred optional substituents include the aforementioned reactive functional groups or moieties, polymer chains and alkyl, (e.g. C1-6 alkyl such as methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), hydroxyalkyl (e.g. hydroxymethyl, hydroxyethyl, hydroxypropyl), alkoxyalkyl (e.g. methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl etc) alkoxy (e.g. C1-6 alkoxy such as methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy), halo, trifluoromethyl, trichloromethyl, tribromomethyl, hydroxy, phenyl (which itself may be further substituted e.g., by C1-6 alkyl, halo, hydroxy, hydroxyC1-6 alkyl, C1-6 alkoxy, haloC1-6alkyl, cyano, nitro OC(O)C1-6 alkyl, and amino), benzyl (wherein benzyl itself may be further substituted e.g., by C1-6 alkyl, halo, hydroxy, hydroxyC1-6alkyl, C1-6 alkoxy, haloC1-6 alkyl, cyano, nitro OC(O)C1-6 alkyl, and amino), phenoxy (wherein phenyl itself may be further substituted e.g., by C1-6 alkyl, halo, hydroxy, hydroxyC1-6 alkyl, C1-6 alkoxy, haloC1-6 alkyl, cyano, nitro OC(O)C1-6 alkyl, and amino), benzyloxy (wherein benzyl itself may be further substituted e.g., by C1-6 alkyl, halo, hydroxy, hydroxyC1-6 alkyl, C1-6 alkoxy, haloC1-6 alkyl, cyano, nitro OC(O)C1-6 alkyl, and amino), amino, alkylamino (e.g. C1-6 alkyl, such as methylamino, ethylamino, propylamino etc), dialkylamino (e.g. C1-6 alkyl, such as dimethylaniino, diethylamino, dipropylamino), acylamino (e.g. NHC(O)CH3), phenylamino (wherein phenyl itself may be further substituted e.g., by C1-6 alkyl, halo, hydroxy hydroxyC1-6 alkyl, C1-6 alkoxy, haloC1-6 alkyl, cyano, nitro OC(O)C1-6 alkyl, and amino), nitro, formyl, -C(O)-alkyl (e.g. C1-6 alkyl, such as acetyl), O-C(O)-alkyl (e.g. C1- 6alkyl, such as acetyloxy), benzoyl (wherein the phenyl group itself may be further substituted e.g., by C1-6 alkyl, halo, hydroxy hydroxyC1-6 alkyl, C1-6 alkoxy, haloC1-6 alkyl, cyano, nitro OC(O)C1-6alkyl, and amino), replacement Of CH2 with C=O, CO2H, C02alkyl (e.g. C1-6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl ester), C02phenyl (wherein phenyl itself may be further substituted e.g., by C1-6 alkyl, halo, hydroxy, hydroxyl C1-6 alkyl, C1-6 alkoxy, halo C1-6 alkyl, cyano, nitro OC(O)C1-6 alkyl, and amino), CONH2, CONHphenyl (wherein phenyl itself may be further substituted e.g., by C1-6 alkyl, halo, hydroxy, hydroxyl C1-6 alkyl, C1-6 alkoxy, halo C1-6 alkyl, cyano, nitro OC(O)C1-6 alkyl, and amino), CONHbenzyl (wherein benzyl itself may be further substituted e.g., by C1-6 alkyl, halo, hydroxy hydroxyl C1-6 alkyl, C1-6 alkoxy, halo C1-6 alkyl, cyano, nitro OC(O)C1-6 alkyl, and amino), CONHalkyl (e.g. C1-6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl amide) CONHdialkyl (e.g. C1-6 alkyl) aminoalkyl (e.g., HN C1-6 alkyl-, C1-6alkylHN-C1-6 alkyl- and (C1-6 alkyl)2N-C1-6 alkyl-), thioalkyl (e.g., HS C1-6 alkyl-), carboxyalkyl (e.g., HO2CC1-6 alkyl-), carboxyesteralkyl (e.g., C1-6 alkylO2CC1-6 alkyl-), amidoalkyl (e.g., H2N(O)CC1-6 alkyl-, H(C1-6 alkyl)N(O)CC1-6 alkyl-), formylalkyl (e.g., OHCC1-6alkyl-), acylalkyl (e.g., C1-6 alkyl(O)CC1-6 alkyl-), nitroalkyl (e.g., O2NC1-6 alkyl-), sulfoxidealkyl (e.g., R(O)SC1-6 alkyl, such as C1-6 alkyl(O)SC1-6 alkyl-), sulfonylalkyl (e.g., R(O)2SC1-6 alkyl- such as C1-6 alkyl(O)2SC1-6 alkyl-), sulfonamidoalkyl (e.g., 2HRN(O)SC1- 6 alkyl, H(C1-6 alkyl)N(O)SCi-6 alkyl-).
In some embodiments, it may be preferable that the aliphatic hydrocarbon group R is optionally substituted with a cyclic ester, cyclic amide, or polyether chain.
The term "halogen" ("halo") denotes fluorine, chlorine, bromine or iodine (fluoro, chloro, bromo or iodo). Preferred halogens are chlorine, bromine or iodine.
The term "carbocyclyl" includes any of non-aromatic monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C3-20 (e.g. C3-1O or C3-8). The rings may be saturated, e.g. cycloalkyl, or may possess one or more double bonds (cycloalkenyl) and/or one or more triple bonds (cycloalkynyl). Particularly preferred carbocyclyl moieties are 5-6-membered or 9-10 membered ring systems. Suitable examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclooctatetraenyl, indanyl, decalinyl and indenyl.
The term "heterocyclyl" when used alone or in compound words includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C3-20 (e.g. C3-10 or C3-8) wherein one or more carbon atoms are replaced by a heteroatom so as to provide a non-aromatic residue. Suitable heteroatoms include O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms. The heterocyclyl group may be saturated or partially unsaturated, i.e. possess one or more double bonds. Particularly preferred heterocyclyl are 5-6 and 9-10 membered heterocyclyl. Suitable examples of heterocyclyl groups may include azridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl, thietanyl, 2H-pyrrolyl, pyrrolidinyl, pyrrolinyl, piperidyl, piperazinyl, morpliolinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, thiomorpholinyl, dioxanyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyrrolyl, tetrahydrothiophenyl, pyrazolinyl, dioxalanyl, thiazolidinyl, isoxazolidinyl, dihydropyranyl, oxazinyl, thiazinyl, thiomorpholinyl, oxathianyl, dithianyl, trioxanyl, thiadiazinyl, dithiazinyl, trithianyl, azepinyl, oxepinyl, thiepinyl, indenyl, indanyl, 3H-indolyl, isoindolinyl, 4H-quinolazinyl, chromenyl, chromanyl, isochromanyl, pyranyl and dihydropyranyl.
The term "heteroaryl" includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, wherein one or more carbon atoms are replaced by a heteroatom so as to provide an aromatic residue. Preferred heteroaryl have 3-20 ring atoms, e.g. 3-10. Particularly preferred heteroaryl are 5-6 and 9-10 membered bicyclic ring systems. Suitable heteroatoms include, O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms. Suitable examples of heteroaryl groups may include pyridyl, pyrrolyl, thienyl, imidazolyl, furanyl, benzothienyl, isobenzothienyl, benzofuranyl, isobenzofuranyl, indolyl, isoindolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, quinolyl, isoquinolyl, phthalazinyl, 1,5-naphthyridinyl, quinozalinyl, quinazolinyl, quinolinyl, oxazolyl, thiazolyl, isothiazolyl, isoxazolyl, triazolyl, oxadialzolyl, oxatriazolyl, triazinyl, and furazanyl.
The term "acyl" either alone or in compound words denotes a group containing the moiety C=O (and not being a carboxylic acid, ester or amide) Preferred acyl includes C(O)-RX, wherein Rx is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue. Examples of acyl include formyl, straight chain or branched alkanoyl (e.g. C1-20) such as, acetyl, propanoyl, butanoyl, 2-methylpropanoyl, pentanoyl, 2,2- dimethylpropanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl and icosanoyl; cycloalkylcarbonyl such as cyclopropylcarbonyl cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexylcarbonyl; aroyl such as benzoyl, toluoyl and naphthoyl; aralkanoyl such as phenylalkanoyl (e.g. phenylacetyl, phenylpropanoyl, phenylbutanoyl, phenylisobutylyl, phenylpentanoyl and phenylhexanoyl) and naphthylalkanoyl (e.g. naphthylacetyl, naphthylpropanoyl and naplithylbutanoyl]; aralkenoyl such as phenylalkenoyl (e.g. phenylpropenoyl, phenylbutenoyl, phenylmethacryloyl, phenylpentenoyl and phenylhexenoyl and naphthylalkenoyl (e.g. naphthylpropenoyl, naphthylbutenoyl and naphthylpentenoyl); aryloxyalkanoyl such as phenoxyacetyl and phenoxypropionyl; arylthiocarbamoyl such as phenylthiocarbamoyl; arylglyoxyloyl such as phenylglyoxyloyl and naphthylglyoxyloyl; arylsulfonyl such as phenylsulfonyl and napthylsulfonyl; heterocycliccarbonyl; heterocyclicalkanoyl such as thienylacetyl, thienylpropanoyl, thienylbutanoyl, thienylpentanoyl, thienylhexanoyl, thiazolylacetyl, thiadiazolylacetyl and tetrazolylacetyl; heterocyclicalkenoyl such as heterocyclicpropenoyl, heterocyclicbutenoyl, heterocyclicpentenoyl and heterocyclichexenoyl; and heterocyclicglyoxyloyl such as thiazolyglyoxyloyl and thienylglyoxyloyl. The Rx residue may be optionally substituted as described herein.
The term "sulfoxide", either alone or in a compound word, refers to a group -S(O)Ry wherein Ry is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl. Examples of preferred Ry include C1-20alkyl, phenyl and benzyl.
The term "sulfonyl", either alone or in a compound word, refers to a group S(O)2-Ry, wherein Ry is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl. Examples of preferred Ry include Ci-2oalkyl, phenyl and benzyl.
The term "sulfonamide", either alone or in a compound word, refers to a group S(O)NRyRy wherein each Ry is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl. Examples of preferred Ry include C1- 20alkyl, phenyl and benzyl. In a preferred embodiment at least one Ry is hydrogen. In another form, both Ry are hydrogen.
The term, "amino" is used here in its broadest sense as understood in the art and includes groups of the formula NR R wherein RA and RB may be any independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl. RA and RB, together with the nitrogen to which they are attached, may also form a monocyclic, or polycyclic ring system e.g. a 3-10 membered ring, particularly, 5-6 and 9- 10 membered systems. Examples of "amino" include NH2, NHalkyl (e.g. C1-2oalkyl), NHaryl (e.g. NHphenyl), NHaralkyl (e.g. NHbenzyl), NHacyl (e.g. NHC(O)C1-20alkyl, NHC(O)phenyl), Nalkylalkyl (wherein each alkyl, for example C1-20, may be the same or different) and 5 or 6 membered rings, optionally containing one or more same or different heteroatoms (e.g. O, N and S).
The term "amido" is used here in its broadest sense as understood in the art and includes groups having the formula C(O)NRΛRB, wherein RA and RB are as defined as above.
Examples of amido include C(O)NH2, C(O)NHalkyl (e.g. C1-2Oalkyl), C(O)NHaryl (e.g.
C(O)NHphenyl), C(O)NHaralkyl (e.g. C(O)NHbenzyl), C(O)NHacyl (e.g.
C(O)NHC(O)C1-20alkyl, C(O)NHC(O)phenyl), C(O)Nalkylalkyl (wherein each alkyl, for example C1-20, may be the same or different) and 5 or 6 membered rings, optionally containing one or more same or different heteroatoms (e.g. O, N and S).
The term "carboxy ester" is used here in its broadest sense as understood in the art and includes groups having the formula CO2R2, wherein Rz may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl. Examples of carboxy ester include CO2C1-20alkyl, CO2aryl (e.g.. CO2phenyl), CO2aralkyl (e.g. CO2 benzyl).
The term "heteroatom" or "hetero" as used herein in its broadest sense refers to any atom other than a carbon atom which may be a member of a cyclic organic group. Particular examples of heteroatoms include nitrogen, oxygen, sulfur, phosphorous, boron, silicon, selenium and tellurium, more particularly nitrogen, oxygen and sulfur.
Those skilled in the art will appreciate that a convenient synthetic route to forming cyclic esters is through a condensation reaction of hydroxycarboxylic acids. As part of the cyclic ester used in accordance with the invention, the α-oxy carbonyl of general formula (I) might therefore be conveniently described as a condensation residue of an a- hydroxycarboxylic acid of general formula (V):
Figure imgf000020_0001
where R is as hereinbefore defined.
The cyclic ester used in accordance with the invention has at least two ester moieties that form part of its cycle. Those skilled in the art will appreciate that the carbonyl group of the α-oxy carbonyl moiety of general formula (I) will in effect provide for one of these ester moieties, and the at least one other ester moiety will be provided by at least one other condensed moiety of a hydroxycarboxylic acid. This at least one further condensed hydroxycarboxylic acid residue may be the same or different to the α-oxy carbonyl moiety of general formula (I), and will complete the cycle of the cyclic ester as represented by the dashed lines in general formula (I).
Thus, a cyclic ester suitable for use in accordance with the invention might have a cyclic structure that is formed from the condensed moieties of at least two α-hydroxycarboxylic acids of general formula (V), or one or more α-hydroxycarboxylic acids of general formula (V) and one or more other hydroxycarboxylic acids. The general structure of a cyclic ester of this type may be conveniently represented by general formula (VI): An1 -Bn2 -An" -Bn4 AnM — Bn1 (VI)
where A is a condensation residue of an ce-hydroxycarboxylic acid of general structure (V), B is the condensation residue of a hydroxycarboxylic acid, each A and each B may be the same or different, each n may be 0 or a positive integer, and i is a positive integer of the series 1, 2, 3, i, wherein n1 >1 and n*+n2 >2.
The cyclic ester of general formula (VI) can therefore be seen to represent a macrocyclic oligoester.
Those skilled in the art will appreciate that the cyclic ester of general formula (VI) serves merely to illustrate the variety of cyclic structures that may be formed in the preparation of cyclic esters. In other words, the cycle size of a cyclic ester may vary depending upon how the cyclic ester is made and from what hydroxycarboxylic acid it is made from. A cyclic ester might also comprise a mixture of different cycle compositions and cycle sizes.
The cyclic esters used in accordance with the invention require at least two ester moieties that form part of its cycle. Those skilled in the art will appreciate that the ester moieties will generally be joined with in the cycle by one or more carbon atoms. There is no particular limitation to the number of ester moieties that may form part of the cycle, but there will generally be no more than about six of such moieties. Accordingly, the cyclic ester might be a dilactone, trilactone, tetralactone, pentalactone, hexalactone, or mixture thereof.
In view of the complexities associated with defining the specific composition of a cyclic ester, it can often be more convenient to refer to the cyclic ester in terms of it being formed from the condensed residue(s) of a particular hydroxycarboxylic acid(s).
Thus, in one embodiment of the invention the cyclic ester used in accordance with the invention comprises as part of its cycle the condensed residue of at least one a- hydroxycarboxylic acid of general formula (V).
In a further embodiment of the invention, the cyclic ester used in accordance with the invention comprises as part of its cycle the condensed residue of at least one a- hydroxycarboxylic acid of general formula (V) and at least one other hydroxycarboxylic acid.
In another embodiment of the invention, the cyclic ester used in accordance with the invention comprises as part of its cycle the condensed residue of at least one a- hydroxycarboxylic acid of general formula (V) and at least one ce-hydroxycarboxylic acid of general formula (VII):
Figure imgf000022_0001
where R1 is an optionally substituted aliphatic hydrocarbon.
When preparing cyclic esters, fatty acids of general formula (V) will generally undergo condensation reactions with itself or other hydroxycarboxylic acids to at least form a dilactone.
Thus, in one embodiment of the invention the cyclic ester comprises a dilactone formed through the condensation of an ce-hydroxycarboxylic acid of a general formula (V).
In a further embodiment of the invention, the cyclic ester comprises a dilactone formed through the condensation of an α-hydroxycarboxylic acid of general formula (V) and another hydroxycarboxylic acid.
In another embodiment of the invention, the cyclic ester comprises a dilactone formed through the condensation of an α-hydroxycarboxylic acid of general formula (V) and an a- hydroxycarboxylic acid of general formula (VII). In that case, the cyclic ester used in accordance with the invention comprises a dilactone of general formula (VIII):
Figure imgf000023_0001
(VIII)
where R and R are the same or different and are as hereinbefore defined.
Where the cyclic ester used in accordance with the invention comprises the optionally substituted aliphatic hydrocarbon R1, R1 will generally be an aliphatic hydrocarbon having
1 to 40, for example 1 to 20 carbon atoms. R1 may be linear or branched, saturated or unsaturated. Where the hydrocarbon is unsaturated, it may be mono- or poly-unsaturated, and includes both cis- and trans-isomers. The hydrocarbon group R1 may be a linear or branched alkyl, alkenyl, or alkynyl group. R1 may also be an acyclic hydrocarbon (i.e. a non-cyclic hydrocarbon). Accordingly, R1 may be the same or different from R. The hydrocarbon R1 may be substituted, for example with a hetero atom containing moiety and/or an aromatic or cyclic moiety. In some embodiments the R1 group is not substituted.
Reagents, equipment, and conditions for manufacturing cyclic esters through the cyclic condensation of hydroxycarboxylic acids are generally well known in the art. Cyclic esters suitable for use in accordance with the invention can advantageously be prepared in a similar manner.
For example, cyclic esters can be prepared by subjecting an ce-hydroxycarboxylic acid of general formula (V), optionally together with one or more different hydroxycarboxylic acids, to heat under vacuum, or by using several methods described in the literature. (Journal of Biomedical Materials Research Part A, Volume 80A, Issue 1, pp 55-65, Polymer Preprints 2005, 46 (2), 1040, Polymer Preprints 2005 (46 (2), 1006).
Cyclic esters suitable for use in accordance with the invention may be conveniently prepared using a variety of α-hydroxycarboxylic fatty acids of general formula (V). Examples of α-hydroxycarboxylic acids of general formula (V) include α-hydroxy valeric acid, α-hydroxy caproic acid, α-hydroxy caprylic acid, α-hydroxy pelargonic acid, α- hydroxy capric acid, α-hydroxy lauric acid, α-hydroxy mytistic acid, α-hydroxy palmitic acid, α-hydroxy margaric acid, α-hydroxy stearic acid, α-hydroxy arachidic acid, α- hydroxy behenic acid, α-hydroxy lignoceric acid, α-hydroxy cerotic acid, α-hydroxy carboceric acid, α-hydroxy montanic acid, α-hydroxy melissic acid, α-hydroxy lacceroic acid, α-hydroxy ceromelissic acid, α-hydroxy geddic acid, α-hydroxy ceroplastic acid, α- hydroxy obtusilic acid, α-hydroxy caproleic acid, α-hydroxy lauroleic acid, α-hydroxy linderic acid, α-hydroxy myristoleic acid, α-hydroxy physeteric acid, α-hydroxy tsuzuic acid, α-hydroxy palmitoleic acid, α-hydroxy sapienic acid, α-hydroxy petroselinic acid, α- hydroxy oleic acid, α-hydroxy elaidic acid, α-hydroxy vaccenic acid, α-hydroxy gadoleic acid, α-hydroxy gondoic acid, α-hydroxy cetoleic acid, α-hydroxy erucic acid, α-hydroxy nervonic acid, α-hydroxy linoleic acid, α-hydroxy γ-linolenic acid, α-hydroxy dihomo-γ- linolenic acid, α-hydroxy arachidonic acid, α-hydroxy α-linolenic acid, α-hydroxy steridonic acid, α-hydroxy nisinic acid, and α-hydroxy Mead Acid.
Examples of hydroxycarboxylic acids that may undergo cyclic condensation with α- hydroxycarboxylic acids of general formula (V) to form cyclic esters suitable for use in accordance with the invention include glycolic acid, lactic acid, 2-hydroxybutanoic acid, 2- hydroxypentanoic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 3- hydroxypentanoic acid, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3- hydroxyoctanoic acid, 3-hydroxy-3-methylbutanoic acid, 3-hydroxy-3-methylpentanoic acid, 3-hydroxy-3-methylheptanoic acid, 3-hydroxy-3-ethylpentanoic acid, 3-hydroxy-3- methylhexanoic acid, 3-hydroxy-3-ethylhexanoic acid, 3-hydroxy-3-propylhexanoic acid, 3-hydroxy-3-methylheptanoic acid, 3-hydroxy-3-ethylheptanoic acid, 3-hydroxy-3- propylheptanoic acid, 3-hydroxy-3-butylheptanoic acid, 3-hydroxy-3-methyloctanoic acid, 3-hydroxy-3-ethyloctanoic acid, S-hydroxy-S-propyloctanoic acid, 3-hydroxy-3- butyloctanoic acid, S-hydroxy-S-pentyloctanoic acid, 4-hydroxybutanoic acid, 4- hydroxypentanoic acid, 4-hydroxyhexanoic acid, 4-hydroxyheptanoic acid, A- hydroxyoctanoic acid, 4-hydroxy-4-methylpentanoic acid, 4-hydroxy-4-methylhexanoic acid, 4-hydroxy-4-ethylhexanoic acid, 4-hydroxy-4-methylheptanoic acid, 4-hydroxy-4- ethylheptanoic acid, 4-hydroxy-4-propylheptanoic acid, 4-hydroxy-4-methyloctanoic acid, 4-hydroxy-4-ethyloctanoic acid, 4-hydroxy-4-propyloctanoic acid, 4-hydroxy-4- butyloctanoic acid, 5-hydroxypentanoic acid, 5-hydroxyhexanoic acid, 5-hydroxyheρtanoic acid, 5-hydroxyoctanoic acid, 5-hydroxy-5-methylhexanoic acid, 5-hydroxy-5- methyl heptanoic acid, 5-hydroxy-5-ethylheptanoic acid, 5-hydroxy-5-methyloctanoic acid, 5-hydroxy-5-ethyloctanoic acid, 5-hydroxy-5-propyloctanoic acid, 6- hydroxyhexanoic acid, 6-hydroxyheptanoic acid, 6-hydroxyoctanoic acid, 6-hydroxy-6- methylheptanoic acid, 6-hydroxy-6-niethyloctanoic acid, 6-hydroxy-6-ethyloctanoic acid, 7-hydroxyheptanoic acid, 7-hydroxyoctanoic acid, 7-hydroxy-7-methyloctanoic acid, 8- hydroxyoctanoic acid, and other aliphatic hydroxycarboxylic acids. These acids can be used singly or as a mixture.
hi accordance with the invention, there is provided a method of preparing a polymer composition, the method comprising melt mixing an aliphatic condensation polymer with the cyclic ester hereinbefore described. Melt mixing can be performed using methods well known in the art. For example, melt mixing may be achieved using continuous extrusion equipment such as twin screw extruders, single screw extruders, other multiple screw extruders and Farell mixers. Semi-continuous or batch processing equipment may also be used to achieve melt mixing. Examples of such equipment include injection moulders, Banbury mixers and batch mixers. Static melt mixing equipment may also be used.
By melt mixing the aliphatic condensation polymer and the cyclic ester, it has been found that the cyclic ester can undergo reaction with condensation polymer such that its ring opened residue becomes incorporated as part of the polymer backbone of the condensation polymer. The polymer composition resulting from the melt mixing process will therefore comprise modified aliphatic condensation polymer having the α-oxy moiety of general foπiiula (I) incorporated as part of its polymeric backbone. The polymer composition may also comprise a proportion of cyclic ester that has not undergone reaction with the aliphatic condensation polymer and/or polymer that has formed through ring opening polymerisation of the cyclic ester.
Those skilled in the art will appreciate that by the α-oxy moiety of general formula (I) being "incorporated" as part of the polymeric backbone of the aliphatic condensation polymer is meant that the cyclic ester ring opens and becomes covalently bound to the polymeric backbone. Without wishing to be limited by theory, it is believed that this process at least involves the ring opened residue being covalently bound to a terminal end of the polymeric backbone, possibly followed by inter and/or intra polymer chain rearrangement of the ring opened residue such that it becomes located at a non-terminal position within the polymeric backbone (e.g. through a transesterification process). In other words, although the ring opened form of the cyclic ester may initially attach to a terminal section of the aliphatic condensation polymer, it may nevertheless rearrange its position within the polymer backbone through a transesterification process.
For example, an aliphatic condensation polymer modified in accordance with the invention using a cyclic ester of general formula (VIII) may comprise within its polymeric backbone the ring opened residue of the cyclic ester as illustrated below in Scheme 1. The modified condensation polymer will of course generally comprise within its polymeric backbone a number of such ring opened residues.
)
Figure imgf000026_0001
Scheme 1: An illustration of an aliphatic condensation polymer modified in accordance with the invention using a cyclic ester of general formula (VIII), where A and B represent the remainder of the condensation polymer. By being incorporated as part the polymeric backbone of the aliphatic condensation polymer in this way, the R group of the α-oxy carbonyl moiety of general formula (I) is believed to modify the properties of the condensation polymer. For example, polylactic acid modified in accordance with the invention has been shown to exhibit improved flexibility. Other pendant moieties derived from the cyclic ester, such as R1 shown above in Scheme 1, may also modify the properties of the condensation polymer.
A condensation catalyst may also be employed in order to enhance the melt reaction between the aliphatic condensation polymer and the cyclic ester. Typical condensation catalysts include Lewis acids such as antimony trioxide, titanium oxide and dibutyl tindilaurate.
Melt mixing of the aliphatic condensation polymer and the cyclic ester may also be conducted in the presence of one or more additives such as fillers, pigments, stabilisers, blowing agents, nucleating agents, and chain coupling and/or branching agents.
Chain coupling and/or branching agents may be used in accordance with the invention to promote an increase in the molecular weight of and/or chain branching in the aliphatic condensation polymer. Such agents include polyfunctional acid anhydrides, epoxy compounds, oxazoline derivatives, oxazolinone derivatives, lactams and related species.
Suitable chain coupling and/or branching agents include one or more of the following:
Polyepoxides such as bis(3,4-epoxycyclohexylmethyl) adipate; N,N-diglycidyl benzamide (and related diepoxies); N,N-diglycidyl aniline and derivatives; N,N-diglycidylhydantoin, uracil, barbituric acid or isocyamiric acid derivatives; N,N-diglycidyl diimides; N,N- diglycidyl imidazolones; epoxy novolaks; phenyl glycidyl ether; diethyleneglycol diglycidyl ether; Epikote 815 (diglycidyl ether of bisphenol A-epichlorohydrin oligomer).
Polyoxazolines/Polyoxazolones such as 2,2-bis(2-oxazoline); 1,3-phenylene bis(2- oxazoline-2), l,2-bis(2-oxazolinyl-2)ethane; 2-phenyl-l,3-oxazoline; 2,2'-bis(5,6-dihydro- 4H-l,3-oxazoline); N,N'-hexamethylenebis (carbamoyl-2-oxazoline; bis[5(4H)- oxazolone); bis(4H-3,lbenzoxazin-4-one); 2,2'-bis(H-3,l-benzozin-4-one).
Polyfunctional acid anhydrides such as pyromellitic dianhydride, benzophenonetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic dianhydride, diphenyl sulphone tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3- methyl-3-cyclohexene-l ,2-dicarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride, bisphenol-A bisether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,3,6,7- naphthalenetetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)sulphone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'- biphenyltetracarboxylic acid, hydroquinone bisether dianhydride, 3,4,9, 10-perylene tetracarboxylic acid dianliydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 3,4- dicarboxy-l,2,3,4-tetrahydro-lnaphthalene-succinic acid dianhydride, bicyclo(2,2)oct-7- ene-2,3,5,6-tetracarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride, 2,2-bis(3,4dicarboxyphenyl)propane dianhydride, 3, 3 ',4,4'- biphenyltetracarboxylic acid dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA), and ethylenediamine tetraacetic acid dianhydride (EDTAh).
It is also possible to use acid anhydride containing polymers or copolymers as the acid anhydride component.
Suitable polyfunctional acid anhydrides include pyromellitic dianhydride, \, 2,3, A- cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride. Most preferably the polyfunctional acid anhydride is pyromellitic dianhydride.
Polyacyllactams such as N,N'-terephthaloylbis(caprolactarn) and N,N'- terephthaloylbis(laurolactam) may also be employed. The polymer composition resulting from the methods of the invention may also be subjected to a subsequent solid state condensation polymerisation process. This further processing step can assist with building the molecular weight of the modified aliphatic condensation polymer and can advantageously be conducted using conventional solid state condensation polymerisation techniques and equipment.
When performing the methods of the invention, it may be convenient to provide the cyclic ester, optionally together with any other additives that are to be used, in the form of a composition that can be used for producing the modified aliphatic condensation polymer. This composition may be provided in the form of a physical blend of the respective components and/or in the form a melt mixed product.
The invention therefore also provides a composition for modifying an aliphatic condensation polymer, the composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I), and/or a product formed by melt mixing a composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I).
The carrier polymer may in fact be the aliphatic condensation polymer that is to be modified in accordance with the invention. In that case the composition may simplistically be a physical blend of the cyclic ester and the polymer, and the method of the invention is preformed by melt mixing that composition.
It may also be desirable to provide at least the cyclic ester in the form of a masterbatch or concentrate which can be subsequently melt mixed with an aliphatic condensation polymer that is to be modified in accordance with the invention.
As used herein, the term "masterbatch" or "concentrate" (to be used synonymously herein) has the common meaning as would be understood by one skilled in the art. With particular reference to the present invention, these terms are therefore intended to mean a composition comprising the cyclic ester and one or more carrier polymers, which composition is to be subsequently let down in an aliphatic condensation polymer in order to perform the methods of the invention.
The masterbatch may be formed by melt mixing the cyclic ester with a carrier polymer that is considered appropriate under the circumstance to be melt mixed with the aliphatic condensation polymer that is to be modified. The carrier polymer may be an aliphatic condensation polymer, for example an aliphatic condensation polymer of the same type as the one that is to be modified.
Where the carrier polymer is an aliphatic condensation polymer, it will be appreciated that the process of making the masterbatch in effect employs the method of the invention. However, by qualifying the product a "masterbatch", it will also be appreciated that the intention is for the masterbatch to be employed in performing the methods of the invention, hi other words, it is the intention that the masterbatch will comprise unreacted cyclic ester that can be subsequently melt mixed with an aliphatic condensation polymer so as to perform the methods of the invention.
A masterbatch formed by melt mixing the cyclic ester with an aliphatic condensation polymer may itself comprise aliphatic condensation polymer that has been modified in accordance with the invention. Melt mixing this modified aliphatic condensation polymer per se with further aliphatic condensation polymer (as will be the case when the masterbatch is melt mixed with an aliphatic condensation polymer) can itself result in the further aliphatic condensation polymer being modified as described herein (e.g. in the case of polyesters, through transesterification reactions).
Aliphatic condensation polymers that may be used as a carrier polymer in the compositions of the invention include those described herein.
Preparing a masterbatch by melt mixing the cyclic ester with an aliphatic condensation polymer and then subsequently melt mixing the masterbatch with an aliphatic condensation polymer is believed to provide a more efficient and effective means of incorporating the ring opended residues as part of the polymeric backbone of the aliphatic condensation polymer.
Those skilled in the art will appreciate that the appropriate temperature at which a given polymer is to be melt mixed with the cyclic ester will vary depending on the type of polymer being employed. Generally, melt mixing of the cyclic ester and the aliphatic condensation polymers will be conducted at a temperature ranging from about 120°C to about 240°C.
Provided that the properties of the aliphatic condensation polymer is modified in at least some way, there is no particular limitation on the amount of cyclic ester that is to be melt mixed with the aliphatic condensation polymer. However, the cyclic ester will generally be used in an amount ranging from about 5 wt.% to about 35 wt.%, preferably 5 wt.% to about 20 wt.%, relative to the mass of the cyclic ester and the aliphatic condensation polymer.
Where the cyclic ester is melt mixed with one or more carrier polymers to prepare a masterbatch, the cyclic ester will generally be used in an amount ranging from about 30 wt.% to about 80 wt.%, relative to the total mass of the cyclic ester and the one or more carrier polymers.
Cyclic esters used in accordance with the methods of the invention can impart to the resulting modified aliphatic condensation polymers properties such as improved flexibility, an alteration in its hardness (either decreased through the incorporation of softer segments provided by the R group, or increased through crosslinking induced from reaction of functional groups within or pendant from the R group), an alteration in its surface properties (e.g. hydrophobicity provided by the R group), altered degradation rates (either decreased through making the polymer overall more hydrophobic (e.g. hydrophobicity provided by the R group) and so less prone to hydrolytic attack, or increased through the introduction via the R group of hydrolytically liable groups to a relatively stable polymer), an alteration in its stiffness (either decreased through the R group breaking up crystallininty, or increased through crosslinking induced from reaction of functional groups within or pendant from the R group), and improved melt viscosity or melt strength resulting directly from the presence of the R group, or through long chain branching induced from reaction of functional groups within or pendant from the R group and the base polymer.
Using the methods of the invention, an aliphatic condensation polymer may also be converted into a thermoset polymer via reaction of functional groups within or pendant from the R group (e.g. oxidative crosslinking of a coating product produced from the modified polymer, or crosslinking reactions where the modified condensation polymer is included in the formulation of a thermoset resin such as a unsaturated polyester, vinyl ester resin, epoxy resin etc).
The stability (e.g. UV) or colour fastness of a modified aliphatic condensation polymer prepared in accordance with the invention may also be improved by tethering an appropriate moiety to the R group (e.g. moieties such as stabilises (e.g. hindered phenols and hindered amine light stabilisers), alkoxy amines, dyes, and bioactive materials).
The modified condensation polymers of this invention can advantageously be utilised in products ranging from: films for packaging applications, injection moulded articles, blow moulded containers, sheet products, thermoformed items, coatings, adhesives, fibres, scaffolds for medical applications including tissue repair and drug delivery.
The present invention will hereinafter be further described with reference to the following non-limiting examples. EXAMPLES
General
Proton NMR spectra were obtained on Bruker AV400 and Bruker AV200 spectrometer, operating at 400 MHz and 200 MHz. All spectra were obtained at 230C unless specified. Chemical shifts are reported in parts per million (ppm) on the δ scale and relative to the chloroform peak at 7.26 ppm (1H) or the TMS peak at 0.00 ppm (1H). Oven dried glassware was used in all reactions carried out under an inert atmosphere (either dry nitrogen or argon). All starting materials and reagents were obtained commercially unless otherwise stated. Removal of solvents "under reduced pressure" refers to the process of bulk solvent removal by rotary evaporation (low vacuum pump) followed by application of high vacuum pump (oil pump) for a minimum of 30 min. Analytical thin layer chromatography (TLC) was performed on plastic-backed Merck Kieselgel KGoOF254 silica plates and visualised using short wave ultraviolet light, potassium permanganate or phosphomolybdate dip. Flash chromatography was performed using 230-400 mesh Merck Silica Gel 60 following established guidelines under positive pressure. Tetrahydrofuran and dichloromethane were obtained from a solvent dispensing system under an inert atmosphere. All other reagents and solvents were used as purchased.
Monomer Synthesis and Characterisation
2-hydroxy fatty acid monomers
General procedure A: Synthesis of saturated 2-hydroxy fatty acids from saturated 2-bromo fatty acids
Saturated 2-bromo fatty acid (1 equivalent) and KOH (4.4 equivalents) were suspended in water (vigorous stirring, 3 ml water per mmol 2-bromo fatty acid) and heated under reflux for 48 h. After 48 h the reaction mixture was cooled to room temperature brought to pH 1 by addition of half concentrated aqueous hydrochloric acid. The mixture was brought to reflux again (10 min), cooled to room temperature and extracted with diethyl ether (3 x, 1A volume of the aqueous layer). The combined organic layers were washed with saturated aqueous ammonium chloride solution (1 x, 1A volume of the organic layer), water (1 x, 1A volume of the organic layer) and brine (1 x, 1A volume of the organic layer) and dried over sodium sulphate. After filtration, the organic solvent was removed under reduced pressure leaving the crude product. If necessary, the crude product was recrystallised from acetone.
Synthesis of 2-hydroxy-hexanoic acid
Figure imgf000034_0001
2-Bromo-hexanoic acid (18.6 g, 95.4 rnmol) and potassium hydroxide (23.5 g, 419.7 mmol) were reacted in 300 ml water accordingly to general procedure A. The crude product was recrystallised from acetone (12.1 g, 91.6 mmol, 96 %).
1H-NMR (CDCl3, 400 MHz): δ[ppm] = 0.85 (tr, 3H, J = 6.6 Hz), 1.20 - 1.49 (m, 4H), 1.60 - 1.72 (m, IH), 1.79 - 1.93 (m, IH), 4.26 (dd, IH, J = 7.3 Hz, 4.2 Hz)
Synthesis of 2-hvdroxy-nonanoic acid
Figure imgf000034_0002
2-Bromo-nonanoic acid (22.6 g, 95.4 mmol) and potassium hydroxide (23.5 g, 419.7 mmol) were reacted in 300 ml water accordingly to general procedure A. The crude product was recrystallised from acetone (15.8 g, 90.6 mmol, 95 %). Synthesis of 2-hydroxy-decanoic acid
Figure imgf000035_0001
2-Bronio-decanoic acid (24.0 g, 95.4 mmol) and potassium hydroxide (23.5 g, 419.7 mmol) were reacted in 300 ml water accordingly to general procedure A. The crude product was recrystallised from acetone (17.1 g, 90.6 mmol, 95 %).
1H-NMR (CDCl3, 400 MHz): δ[ppm] = 0.88 (tr, 3H, J = 6.6 Hz), 1.23 - 1.56 (m, 12H), 1.63 - 1.77 (m, IH), 1.80 - 1.94 (m, IH), 4.25 (dd, IH, J = 7.4 Hz, 4.1 Hz)
1H-NMR (CDCl3, 400 MHz): δ[ppm] = 0.88 (tr, 3H, J = 6.7 Hz), 1.28 - 1.53 (m, 8H)5 1.65 - 1.74 (m, IH), 1.81 - 1.91 (m, IH), 4.27 (dd, IH, J = 7.5 Hz, 4.2 Hz)
Synthesis of 2-hvdroxy-hexadecanoic acid
Figure imgf000035_0002
2-Bromo-hexadecanoic acid acid (10.0 g, 29.8 mmol) and potassium hydroxide (7.4 g, 131.1 mmol) were reacted in 90 ml water accordingly to general procedure A (8.0 g, 29.5 mmol, 99 %).
1H-NMR ((CDs)2CO, 200 MHz): δ[ppm] = 0.91 (tr, 3H, J = 6.1 Hz), 1.17 - 1.55 (m, 24 H), 1.58 - 1.90 (m, 2H), 4.17 (dd, IH, J = 7.1 Hz, 4.2 Hz) Svnthesis of 2-hydroxy-octadecanoic acid
Figure imgf000036_0001
2-Bromo-octadecanoic acid acid (4.06 g, 11.2 mmol) and potassium hydroxide (2.8 g, 49.4 mmol) were reacted in 32 ml water accordingly to general procedure A. The crude product was recrystallised from acetone (3.3 g, 10.9 mmol, 97 %).
1H-NMR ((CD3)2SO, 400 MHz): δ[ppm] = 0.89 (tr, 3H, J = 6.6 Hz), 1.20 - 1.43 (m, 28 H), 1.47 - 1.69 (m, 2H), 3.94 (dd, IH, J = 7.5 Hz, 4.6 Hz), 4.93 - 5.24 (br, IH), 12.10 - 12.63 (br, IH)
Synthesis of (Z)-2-hvdroxyoctadec-9-enoic acid
Figure imgf000036_0002
Anhydrous THF (70 ml) and diisopropylamine 5.0 ml, 35.4 mmol) were added to a dry flask flushed with argon and cooled to -30°C. n-Buthyllithium (1.6 M in hexane) (23.3 ml, 37.2 mmol) was added followed by (Z)-octadec-9-enoic acid (5.0 g, 17.7 mmol) in dry THF (20 ml)while maintaining the temperature at -30°C. Dianion formation was completed by heating the solution to 50°C for 30 min and then cooling to room temperature. Oxygen was bubbled directly into the dianion solution at room temperature for 30 min. The reaction mixture was diluted with water (200 ml), acidified with IN aqueous hydrochloric acid (pH 2) and extracted with diethylether 3 x 100 ml). The combined organic layers were washed with brine (1 x 100 ml) and dried over sodium sulphate. After filtration, the organic solvent was removed under reduced pressure leaving the crude product. The crude product was recrystallised from hexane (4.6 g, 15.4 mmol, 87 %). 1H-NMR (CDCl3, 400 MHz): δ[ppm] = 0.88 (tr, 3H, J = 6.7 Hz), 1.22 - 1.53 (m, 20 H), 1.65 - 1.76 (m, IH), 1.80 - 1.92 (m, IH), 1.96 - 2.06 (m, 4H), 4.28 (dd, IH, J = 7.5 Hz, 4.2 Hz), 5.29 - 5.39 (m, 2H)
Synthesis of 2-hydroxyundec-lO-enoic acid
Figure imgf000037_0001
Anhydrous THF (70 ml) and diisopropylamine 5.0 ml, 35.4 mmol) were added to a dry flask flushed with argon and cooled to -30°C. n-Buthyllithium (1.6 M in hexane) (23.3 ml, 37.2 mmol) was added followed by undec-10-enoic acid (3.26 g, 17.7 mmol) in dry THF (20 ml) while maintaining the temperature at -30°C. Dianion formation was completed by heating the solution to 50°C for 30 minand then cooling to room temperature. Oxygen was bubbled directly into the dianion solution at room temperature for 30 min. The reaction mixture was diluted with water (200 ml), acidified with IN aqueous hydrochloric acid (pH 2) and extracted with diethylether 3 x 100 ml). The combined organic layers were washed with brine (1 x 100 ml) and dried over sodium sulphate. After filtration, the organic solvent was removed under reduced pressure leaving the crude product. The crude product was recrystallised from hexane (2.87 g, 14.3 mmol, 81 %).
1H-NMR (CDCl3, 400 MHz): δ[ppm] = 5.86 - 5.76 (m, IH), 5.03 - 4.90 (m, 2H), 4.28 (dd, IH, J1 = 7.5 Hz, J2 = 4.2 Hz), 2.03 (dd, 2H, J1 = 14.2 Hz, J2 = 6.8 Hz), 1.92 - 1.80 (m, IH), 1.75 - 1.64 (m, IH), 1.56 - 1.25 (m, 10H)
Symmetric and asymmetric lactones from 2-hydroxy fatty acids
Synthesis of 3-methyl-6-tetradecyl-l,4-dioxane-2.5-dione [C3:C16:0 Lactone]
Figure imgf000038_0001
To 65.0 g (0.24 mol) 2-hydroxy-hexadecanoic acid 26.6 ml (0.25 mol) 2-bromopropionyl bromide were slowly added and stirred at 100°C under nitrogen flow for 12 h while evolving HBr was neutralized. 1.9 1 acetone and 66.6 ml (0.478 mol) triethylamine were added to the mixture and the solution was stirred at 60°C for 3 h. After filtration of the triethylammonium bromide salts acetone and triethylamine were distilled off and the resulting mixture was dissolved in 1.0 1 ethylacetate:hexane mixture (1:2). After filtration over silica gel, the solvents were distilled off and the remaining crude product was recrystallised from hexane at -20°C.
1H-NMR (CDCl3, 400 MHz): δ[ppm] = 0.87 (tr, 3H, J = 6.3 Hz), 1.17 - 1.63 (m, 26 H), 1.66 (d, J = 6.7 Hz) and 1.70 (d, J = 6.7 Hz) (3H from 2 diastereomers), 1.89 - 2.17 (m, 2H), 4.82 - 4.95 (m, IH), 4.96 - 5.08 (m, IH)
Synthesis of (Z)-3-fliexadec-7-enyl)-6-methyl- 1.4-dioxane-2,5-dione [C3:C18:1 Lactonel
Figure imgf000038_0002
1.00 g (3.35 mmol) of 2-hydroxy-octadec-9-enoic acid and 1.16 g (5.36 mmol) of 2- bromo-propionyl bromide were dissolved in 100 ml of dry THF (under argon) and cooled to 0°C. Triethylamine (1.36 g, 13.4 mmol) was added dropwise under mechanical stirring. The reaction mixture was allowed to stir 3h at 0°C and then at room temperature over night. A white precipitate formed which was romoved by filtration and the filtrate was condensed under reduced pressure. The resulting crude product was dissolved in dry acetone (200 ml), triethylamine (1.36 g, 13.4 mmol) was added and the reaction mixture was heated to reflux for 12 h. After that the solvent was removed under reduced pressure, the crude product was redissolved in diethyl ether (100 ml), successively extracted with 0.5 M aqueous HCl solution (100 ml) and saturated aqueous NaHCO3 solution and dried over MgSO4. The crude product was purified via column chromatography (0.80 g, 2.24 mmol, 67 %).
1H-NMR (CDCl3, 400 MHz): δ[ppm] = 0.86 (tr, 3H, J = 6.3 Hz), 1.20 - 1.60 (m, 20H), 1.65 (d, J = 6.3 Hz), 1.68 (d, J = 6.3 Hz) (3H from 2 diastereomers), 1.89 - 2.11 (m, 6H), 4.85 - 4.93 (m, IH), 4.98 - 5.06 (m, IH), 5.28 - 5.38 (m, 2H)
Synthesis of 3,6-diheptyl-l,4-dioxane-2,5-dione [C9:C9 Lactonel
Figure imgf000039_0001
A mixture of 2.0 g (11.5 mmol) of 2-hydroxynonanoic acid and 0.20 g (1.2 mmol) of p- toluenesulfonic acid in 200 ml toluene was heated at reflux for 24 h and the forming water removed continuously by using a Dean-Stark apparatus. The toluene was distilled off and the resulting mixture was dissolved in 200 ml ethyl acetate-hexane mixture (1:2) and filtered over silica gel. After removal of the solvents, the residue was dissolved in diethyl ether. The solution was washed with sodium hydrogen carbonate (saturated solution) and dried over magnesium sulphate. The product was recrystallised from diethylether (1.1 g, 3.6 mmol, 62%).
1H-NMR (CDCl3, 400 MHz): δ[ppm] = 0.89 (tr, 3H5 J = 6.4 Hz), 1.19 - 1.62 (m, 10H),1.87 - 2.21 (m, 2H)5 4.83 - 4.94 (m, 2H) General procedure B: Synthesis of dilactones of 2-hydroxy acids
A mixture of 2-hydroxy acid was heated under vaccuum at 120 °C - 180 0C for 16 h - 24 h. Under these conditions the forming water was removed continuously. The obtained product was used without further purification.
Synthesis of 3,6-dibutyl-l,4-dioxane-2,5-dione
Figure imgf000040_0001
2-hydroxy hexanoic acid (20 g, 151.3 mmol) was reacted accordingly to general procedure C.
1H-NMR (CDCl3, 200 MHz): δ[ppm] = 5.24 - 4.99 (m, 2H), 2.06 - 1.79 (m, 4H), 1.61 - 1.36 (m, 8H), 0.90 (tr, 6H, J = 6.8 Hz)
Synthesis of 3,6-dioctyl- 1 ,4-dioxane-2,5-dione
Figure imgf000040_0002
2-hydroxy decanoic acid (20 g, 106.2 mmol) was reacted accordingly to general procedure C.
1H-NMR (CDCl3, 200 MHz): δ[ppm] = 5.22 - 5.07 (m, 2H), 2.04 - 1.88 (m, 4H), 1.62 - 1.27 (m, 24H), 0.87 (tr, 6H, J = 5.8 Hz) Synthesis of 3,6-di(non-8-enyl)- 1 ,4-dioxane-2,5-dione
Figure imgf000041_0001
2-hydroxy undecenoic acid (20 g, 99.9 mmol) was reacted accordingly to general procedure C.
1H-NMR (CDCl3, 400 MHz): δ[ppm] = 5.84 - 5.71 (m, 2H), 5.21 - 4.82 (m, 6H), 2.15 - 1.87 (m,8H), 1.57 - 1.29 (m, 20H)
Synthesis of3,6-ditetradecyl-l,4-dioxane-2,5-dione
Figure imgf000041_0002
2-hydroxy hexadecanoic acid (20 g, 73.4 mmol) was reacted accordingly to general procedure C.
1H-NMR (CDCl3, 200 MHz): δ[ppm] = 5.24 - 4.79 (m, 2H), 2.07 - 1.73 (m, 4H), 1.53 - 1.09 (m,48H), 0.87 (tr, 6H, ] = 6.1 Hz) Synthesis of 3 ,6-di((Z)-hexadec-7-enyl)- 1 ,4-dioxane-2,5 -dione
Figure imgf000042_0001
2-hydroxy oleic acid (20 g, 67.0 mmol) was reacted accordingly to general procedure C.
1H-NMR (CDCl3, 200 MHz): δ[ppm] = 5.40 - 5.26 (m, 4H), 5.14 - 5.06 (m, 2H), 2.14 - 1.75 (m, 8H), 1.54 - 1.07 (m, 40H), 0.87 (tr, 6H, J = 6.1 Hz)
Polymers Used for Melt Mixing
The following polymers were used to produce the examples for melt mixing with the lactones:
PLA = Polylactic acid - Natureworks 305 ID, supplied by Cargill, USA Nylon 11 = Rilsan BESNO TL (Check?), supplied by Arkema, France
Catalyst
Tin (II) 2 Ethyl Hexanoate, supplied by Sigma Aldrich Dibutyl tin di-laurate (DBTDL), supplied by Sigma Aldrich
Methods for Melt Mixing
(A) Twin Screw Extruder - Liquid injection of Lactone. [EL]
Melt mixing reactions were carried out in a Thermo Prism 16mm twin screw extruder having a L/D of 40:1 fitted with segmented screws and individually heated barrel segments (see Scheme 2) Prism 16mm
Co -Rotating Screw
Figure imgf000043_0001
Scheme 2: Schematic setup of the Prism twin screw extruder use to melt modify the polymers with the lactone.
The lactone monomer was dried under vacuum at 80C with stirring. The lactone was mixed with 0.1 wt% of the liquid catalyst and then charged into the heated barrel (80C) of an ISCO 500D syringe pump fitted with a heated line to dispense the lactone into the barrel of the twin screw extruder.
The gravimetric output of the ISCO syringe pump was calibrated at a number of relevant volumetric throughput rates prior to connecting to the extruder.
The polymer was dried in a small scale hopper drier using dry air at temperatures according to the manufacturer's recommendations. All samples were dried to < lOOppm water, as measured using an Arizona Instruments moisture analyser.
The dried polymer was fed to the extruder via a Barrell single screw volumetric feeder. The feeder and extruder hopper were flushed with dry air to prevent moisture ingress. The gravimetric output of the feeder and extruder were monitored by collecting samples before and after collecting samples.
The extruder was fitted with a lmm rod die and operated at a throughput of rate of approximately 25g/hour. The exact throughput rate was determined for each sample. The extraded samples which were subsequently melt pressed were collected in sample jars purged with dry nitrogen. Melt pressing was carried in an IHMS melt press ( 250 by 250mm plattern) fitted with brass plates through water could be passed to cool the sample after pressing. Samples were pressed between Teflon sheets. A 150 by 150 by 0.150 mm shim plate was used for the melt pressing.
Extruded strand samples were also collected for each composition.
(B) Twin Screw Extruder - Coating of Lactone onto polymer. [EC]
Melt mixing reactions were carried out in a Thermo Prism 16mm twin screw extruder fitted with segmented screws and individually heated barrel segments, [see Figure 1] .
The lactone monomer and catalyst was dissolved in the minimum quantity of solvent (hexane). The solution was coated onto cryo ground polymer powder. The excess solvent was removed by rotovap and vacuum oven.
The lactone coated polymer was dried in a small scale hopper drier using dry air at temperatures according to the manufacturer's recommendations. All samples were dried to < lOOppm water, as measured using an Arizona Instruments moisture analyser.
The dried lactone coated polymer was fed to the extruder via a Barrell single screw volumetric feeder. The feeder and extruder hopper were flushed with dry air to prevent moisture ingress. The gravimetric output of the feeder and extruder were monitored by collecting samples before and after collecting samples.
The extruder was fitted with a lmm rod die and operated at a throughput of rate of approximately 25g/hour. The exact throughput rate was determined for each sample.
The extruded samples which were subsequently melt pressed were collected in sample jars purged with dry nitrogen. Melt pressing was carried in an IHMS melt press ( 250 by 250mm plattern) fitted with brass plates through water could be passed to cool the sample after pressing. Samples were pressed between Teflon sheets. A 150 by 150 by 0.150 mm shim plate was used for the melt pressing.
Extruded strand samples were also collected for each composition.
(C) Melt mixing in round bottom flasks [RBF]
Polymers were dried using the same methodology as was used for the extrusion samples. The lactone samples were vacuum dried prior to use.
The 25ml round bottom flasks used for the experiments were cleaned, fitted with large magnetic spinbars and dried in an oven set at 80C. Upon removal from the oven the flasks were stoppered and allowed to cool. Upon opening the flasks to add the reagents, the flasks were flushed with dry nitrogen.
Approximately 5g of the selected polymer was added to each flask, the required amount of lactone and 3 drops of Tin (II) 2 Ethyl Hexanoate catalyst.
The flasks were then placed in a silicone oil bath on top of a magnetic stirrer hotplate. The oil temperature was controlled to the desired temperature (210C for PLA, 240C for Nylon 11) and monitored via a calibrated thermometer.
Samples were allowed to heat and stir for 20min. At the 5min, 10 and 15min points the tops were removed and the samples were stirred more vigorously with spatula while being gently flushed with dry nitrogen.
At the completion of the reaction the samples were stoppered and allowed to cool. For melt pressing samples were reheated in a vacuum oven, subsamples were removed from the flasks and were melt pressed using the same procedure as was used for the extrusion samples. (D) Melt mixing in round bottom flasks - method with overhead stirring [RBF-2]
Polymers were dried using the same methodology as was used for the extrusion samples. The lactone samples were vacuum dried prior to use.
The 100ml round bottom flasks used for the experiments were cleaned and dried in an oven set at 80C. Upon removal from the oven the flasks were stoppered and allowed to cool. Upon opening the flasks to add the reagents, the flasks were flushed with dry nitrogen. The flasks were then fitted with metal stirrers having two blades. The stirrers were connected to overhead drive motors. The stirrers were held in place by a glass adapter fitted with a Teflon bearing fitted with a rubber seal. The glass adaptor was also fitted with a water cooled Leibig condenser and a separate nitrogen inlet to prevent moisture ingress.
Approximately 2Og of the selected polymer was added to each flask, the required amount of lactone and 20 drops of DBTDL catalyst.
The flasks fitted with the adaptors, condensers and stirrers were then placed in a silicone oil bath on top of a magnetic stirrer hotplate. The oil temperature was controlled to the desired temperature ( 200C for PLA, 250C for Nylon 11) and monitored via a calibrated thermometer.
Samples were allowed to heat and stir for times up to 240min. The rate of stirring was set between 100 to 200 rpm. The exact rate adjusted to give good mixing to best provide the incorporation of the lactone modifier.
At the completion of the reaction the stirrers and condensers were removed and samples were poured from the flasks under a blanket of dry nitrogen. The samples were then allowed to cool. For melt pressing samples were reheated in a vacuum oven, sub-samples were removed for analysis from the flasks and were melt pressed using the same procedure as was used for the extrusion samples.
Characterisation of Polymers
Polymer samples were characterised by a number of techniques as described below.
NMR- Nuclear Magnetic Resonance
Proton NMR spectra were obtained on Bruker AV400 and Bruker AV200 spectrometer, operating at 400 MHz and 200 MHz. All spectra were obtained at 230C unless specified. Chemical shifts are reported in parts per million (ppm) on the δ scale and relative to the chloroform peak at 7.26 ppm (1H) or the TMS peak at 0.00 ppm (1H).
Tensile Testing
Tensile testing was carried out using an Instron 5500R machine. Melt pressed film samples were cut into tensile bars (Length = 31.5mm, Width= 4.2mm, Gauge length= 15mm) using a compression cutter. Samples were conditioned in a controlled temperature and humidity room for 48 hours prior to testing. Samples were tested according to ASTM 882 at a crosshead speed of 7.5mm/min.
Differential Scanning Calorimetry
The thermal behaviour of the samples was determined by differential scanning calorimetry ( DSC) using a Mettler Toloedo DSC 85 Ie DSC system. Samples were weighed into 40ul pans and lids were crimped onto the pans. A hole was then made in the lids with a 20 gauge needle to prevent pressurisation. All scans were carried out at a scanning rate of 10 degrees Celsius (C) per minute. Scan were typically as follows; (i) heating from 20 to either 180C (polyesters) or 220C (polyamides); (ii) then the pans were held at the elevated temperature for 3 minutes;(iii) then cooled at 10 C/min. to -20 C; (iv) samples were held at the sub-ambient temperature for 3 minutes and (v) then the samples were heated to the elevated temperature (180 or 220C) at a rate of 10 C/min. The transition temperatures, and enthalpies for crystallisation and melting were determined for each samples. The DSC was calibrated using an Indium standard.
Modified Polymers
Figure imgf000048_0001
Figure imgf000049_0001
a — mole% modifier' calculated as moles of modifier fatty acid. The moles of alpha hydroxyl fatty acid introduced is a multiple of the size of the lactone. For di-lactones 2 moles of acid are introduced per mole of lactone.
Masterbatch Examples
As an example of demonstrating that the modified material can be used as a masterbatch, a amount of the modified polymer (Example 15), was dried and was melt mixed with as an equal wt:wt basis with PLA pellets using the method RBF-2.
Figure imgf000050_0003
ANALYSIS
Modification with symmetric dilactones - NMR analysis
The signal of the hydrogen between carbonyl and alcohol functionality can be used to determine the level of incorporation of symmetric dilactones into the nylon chain. Incorporation of a modifying unit causes a shift in this signal.
multiplet between 5.45 ppm and 5.10 ppm change in shift after incorporation ppm chain
Figure imgf000050_0001
chain
Figure imgf000050_0002
The minimum (mole %) of modifier attached to nylon is calculated through the equation: minimum (mole %) of modifier attached to nylon = Integral 5.10 ppm to 5.05 ppm/ Integral 5.45 ppm - 5.05 ppm
The signal of the PLA methyl group can be used to determine the level of incorporation of symmetric dilactones into the PLA chain. Incorporation of a modifying unit causes a shift in this signal.
Figure imgf000051_0001
The minimum (mole %) of lactic acid attached to modifier lactone is calculated through the equation:
minimum (mole %) of lactic acid attached to modifier lactone = Integral 1.75 ppm to 1.64 ppm/ Integral 1.75 ppm - 1.48 ppm
Minimum incorporation of modifiers - by NMR
Figure imgf000051_0002
DSC
Figure imgf000052_0001
# DSC data taken from first heat cycle of sample a - PLA and Nylon 11 controls are for samples which have been melt mixed under the same conditions. Times represent melt mixing times, b - Major peak in bold TENSILE
Figure imgf000053_0001
Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Claims

1. A method of preparing a polymer composition, the method comprising melt mixing an aliphatic condensation polymer with a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of a general formula (I):
Figure imgf000054_0001
where R is an optionally substituted aliphatic hydrocarbon having 3 or more carbon atoms.
2. The method according to claim 1, wherein the aliphatic hydrocarbon group R comprises 3 to about 40 carbon atoms.
3. The method according to claim 1 or 2, wherein the aliphatic hydrocarbon group R is unsaturated.
4. The method according to any one of claims 1 to 3, wherein the aliphatic hydrocarbon group R is an optionally substituted acyclic aliphatic hydrocarbon.
5. The method according to any one of claims 1 to 4, wherein at least two α-oxy carbonyl moieties of general formula (I) form the cycle of the cyclic ester.
6. The method according to any one of claims 1 to 5, wherein the α-oxy carbonyl moiety of general formula (I) is a condensed residue of an α-hydroxy acid selected from a- hydroxy valeric acid, α-hydroxy caproic acid, α-hydroxy caprylic acid, α-hydroxy pelargonic acid, α-hydroxy capric acid, α-hydroxy lauric acid, α-hydroxy mytistic acid, a- hydroxy palmitic acid, α-hydroxy margaric acid, α-hydroxy stearic acid, α-hydroxy arachidic acid, α-hydroxy behenic acid, α-hydroxy lignoceric acid, α-hydroxy cerotic acid, α-hydroxy carboceric acid, α-hydroxy montanic acid, α-hydroxy melissic acid, α-hydroxy lacceroic acid, α-hydroxy ceromelissic acid, α-hydroxy geddic acid, α-hydroxy ceroplastic acid, α-hydroxy obtusilic acid, α-hydroxy caproleic acid, α-hydroxy lauroleic acid, α- hydroxy linderic acid, α-hydroxy myristoleic acid, α-hydroxy physeteric acid, α-hydroxy tsuzuic acid, α-hydroxy palmitoleic acid, α-hydroxy sapienic acid, α-hydroxy petroselinic acid, α-hydroxy oleic acid, α-hydroxy elaidic acid, α-hydroxy vaccenic acid, α-hydroxy gadoleic acid, α-hydroxy gondoic acid, α-hydroxy cetoleic acid, α-hydroxy erucic acid, α- hydroxy nervonic acid, α-hydroxy linoleic acid, α-hydroxy γ-linolenic acid, α-hydroxy dihomo-γ-linolenic acid, α-hydroxy arachidonic acid, α-hydroxy α-linolenic acid, α- hydroxy steridonic acid, α-hydroxy nisinic acid, and α-hydroxy Mead Acid.
7. The method according to any one of claims 1 to 6, wherein the α-oxy carbonyl moiety of general formula (I) forms the cycle of the cyclic ester together with at least one condensed residue of a hydroxycarboxylic acid selected from glycolic acid, lactic acid, 2- hydroxybutanoic acid, 2-hydroxypentanoic acid, 3-hydroxypropanoic acid, 3- hydroxybutanoic acid, 3-hydroxypentanoic acid, 3-hydroxyhexanoic acid, 3- hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxy-3-methylbutanoic acid, 3- hydroxy-3-methylpentanoic acid, 3-hydroxy-3-methylheptanoic acid, 3-hydroxy-3- ethylpentanoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-3-ethylhexanoic acid, 3-hydroxy-3-propylhexanoic acid, 3-hydroxy-3-methylheptanoic acid, 3-hydroxy-3- ethylheptanoic acid, 3 -hydroxy-3 -propyl heptanoic acid, 3-hydroxy-3-butylheptanoic acid, 3-hydroxy-3-methyloctanoic acid, 3-hydroxy-3-ethyloctanoic acid, 3-hydroxy-3- propyloctanoic acid, 3-hydroxy-3-butyloctanoic acid, 3-hydroxy-3-pentyloctanoic acid, A- hydroxybutanoic acid, 4-hydroxypentanoic acid, 4-hydroxyhexanoic acid, A- hydroxyheptanoic acid, 4-hydroxyoctanoic acid, 4-hydroxy-4-methylρentanoic acid, A- hydroxy-4-methylhexanoic acid, 4-hydroxy-4-ethylhexanoic acid, 4-hydroxy-4- methylheptanoic acid, 4-hydroxy-4-ethylheptanoic acid, 4-hydroxy-4-propyl heptanoic acid, 4-hydroxy-4-methyloctanoic acid, 4-hydroxy-4-ethyloctanoic acid, 4-hydroxy-4- propyloctanoic acid, 4-hydroxy-4-butyloctanoic acid, 5-hydroxypentanoic acid, 5- hydroxyhexanoic acid, 5-hydroxyheptanoic acid, 5-hydroxyoctanoic acid, 5-hydroxy-5- methylhexanoic acid, 5-hydroxy-5-methylheptanoic acid, 5-hydroxy-5-ethylheptanoic acid, S-hydroxy-S-methyloctanoic acid, S-hydroxy-S-ethyloctanoic acid, 5-hydroxy-5- propyloctanoic acid, 6-hydroxyhexanoic acid, 6-hydroxyheptanoic acid, 6- hydroxyoctanoic acid, 6-hydroxy-6-methylheptanoic acid, ό-hydroxy-ό-methyloctanoic acid, 6-hydroxy-6-ethyloctanoic acid, 7-hydroxyheptanoic acid, 7-hydroxyoctanoic acid, 7- hydroxy-7-methyloctanoic acid, and 8 -hydroxyoctanoic acid.
8. The method according to any one of claims 1 to 4, wherein the cyclic ester comprises a cyclic ester of general formula (VIII) :
Figure imgf000056_0001
(VIII)
where R1 is an optionally substituted aliphatic hydrocarbon.
9. The method according to claim 8, wherein R = R1.
10. The method according to any one of claims 1 to 9, wherein the aliphatic condensation polymer is selected from polyesters, polyamides, copolymers thereof, and blends thereof.
11. The method according to claim 10, wherein the polyesters are poly(hydroxyalkanoates).
12. The method according to claim 11, wherein the poly(hydroxyalkanoates) are selected from homo- and copolymers of poly(3-hydroxybutyrate), poly(4- hydroxybutyrate), poly(3-hydroxyvalerate), poly(lactic acid), poly(3-hydroxypropanoate), poly(4-hydropcntanoate), poly(3-hydroxypentanoate), poly(3-hydroxyhexanoate), poly(3- hydroxyheptanoate), poly(3-hydroxyoctanoate), polydioxanone, polycaprolactone, polyglycolic acid, and blends thereof.
13. The method according to claim 10, wherein the polyesters are a reaction product of one or more alkyldiols with one or more alkyldicarboxylic acids or their acyl derivatives.
14. The method according to claim 13, wherein the polyesters are a reaction product of (a) one or more alkyldicarboxylic acids selected from succinic acid, adipic acid, 1,12 dicarboxydodecane, fumaric acid, and maleic acid, and (b) one of more alkyldiols selected from ethylene glycol, polyethylene glycol, 1,2-propane diol, 1,3-propanediol, 1,2- propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and polypropylene glycol.
15. The method according to claim 14, wherein the polyesters are selected from polybutylenesuccinate homopolymer, polybutylene adipate homopolmer, polybutyleneadipate-succinate copolymer, polyethylenesuccinate-adipate copolymer, polyethylene adipate homopolymer, and blends thereof.
16. The method according to claim 10, wherein the polyamides are a reaction product of one or more alkyldiamines with one or more alkyldicarboxylic acids.
17. The method according to claim 16, wherein the polyamides are selected from pory(tetramethylene adipamide) (nylon 4,6), poly(hexamethylene adipamide) (nylon 6,6), poly(hexamethylene azelamide) (nylon 6,9), poly(hexamethylene sebacamide) (nylon 6,10), poly(heptamethylene pimelamide) (nylon 7,7), poly(octamethylene suberamide) (nylon 8,8), poly(nonamethylene azelamide) (nylon 9,9), and poly(decamethylene azelamide) (nylon 10,9).
18. The method according to claim 10, wherein the polyamides are a polymerised product of one or more alkylarnino acids and/or lactam derivative thereof.
19. The method according to claim 18, wherein the polyamides are selected from poly(4-aminobutyric acid) (nylon 4), poly(6-aminohexanoic acid) (nylon 6), poly(7-amino- heptanoic acid) (nylon 7), poly(8-aminoocatanoic acid) (nylon 8), poly(9-aminononanoic acid) (nylon 9), poly(10-aminodecanoic acid) (nylon 10), poly(l l-aminoundecanoic acid) (nylon 11), poly(12-aminododecanoic acid) (nylon 12), and blends thereof.
20. The method according to any one of claims 1 to 19, wherein about 5.wt% to about 35 wt. % of the cyclic ester is melt mixed with the aliphatic condensation polymer, relative to the total mass of the ester and the aliphatic condensation polymer.
21. The method according to any one of claims 1 to 19, wherein the cyclic ester is provided in the form of a composition comprising one or more carrier polymers and the cyclic ester and/or a product formed by melt mixing a composition comprising one or more carrier polymers and the cyclic ester.
22. The method according to claim 21, wherein the cyclic ester composition is prepared by melt mixing a composition comprising the cyclic ester and the one or more carrier polymers.
23. The method according to claim 21 or 22, wherein the one or more carrier polymers is an aliphatic condensation polymer of the same type as the aliphatic condensation polymer used in claim 1.
24. The method according to claim 23, wherein about 30.wt% to about 80 wt. % of the cyclic ester is melt mixed with the aliphatic condensation polymer, relative to the total mass of the ester and aliphatic condensation polymer in the cyclic ester composition.
25. A polymer composition prepared by a method according to any one of claims 1 to 24.
26. A polymer composition for modifying an aliphatic condensation polymer, the composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I), and/or a product formed by melt mixing a composition comprising one or more carrier polymers and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I):
Figure imgf000059_0001
where R is an optionally substituted aliphatic hydrocarbon having 3 or more carbon atoms.
27. The polymer composition according to claim 26, wherein the one or more carrier polymers is an aliphatic condensation polymer.
28. The polymer composition according to claim 26 or 27, wherein the aliphatic condensation polymer is selected from polyesters, polyamides, copolymers thereof, and blends thereof.
29. The polymer composition according to any one of claims 26 to 28, wherein at least two α-oxy carbonyl moieties of a general formula (I) form the cycle of the cyclic ester.
30. The polymer composition according to any one of claims 26 to 28, wherein the cyclic ester comprises a cyclic ester of general formula (VIII):
Figure imgf000060_0001
(VIII)
where R1 is an optionally substituted aliphatic hydrocarbon.
31 The polymer composition according to claim 30, wherein R = R1.
32. A polymer composition comprising an aliphatic condensation polymer and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I), and/or a product formed by melt mixing a composition comprising an aliphatic condensation polymer and a cyclic ester having at least two ester moieties that form part of its cycle, wherein said cycle comprises an α-oxy carbonyl moiety of general formula (I):
Figure imgf000060_0002
where R is an optionally substituted aliphatic hydrocarbon having 3 or more carbon atoms.
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