WO2024076749A1 - Compostable composition - Google Patents
Compostable composition Download PDFInfo
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- WO2024076749A1 WO2024076749A1 PCT/US2023/034665 US2023034665W WO2024076749A1 WO 2024076749 A1 WO2024076749 A1 WO 2024076749A1 US 2023034665 W US2023034665 W US 2023034665W WO 2024076749 A1 WO2024076749 A1 WO 2024076749A1
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- WIPO (PCT)
- Prior art keywords
- composition
- polycaprolactone
- article
- comprised
- amount
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 48
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 46
- 239000004626 polylactic acid Substances 0.000 claims abstract description 46
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 44
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims description 14
- 235000013305 food Nutrition 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- -1 fatty acid salt Chemical class 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical group [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims 4
- 229940123973 Oxygen scavenger Drugs 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229940049964 oleate Drugs 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical group CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 235000012424 soybean oil Nutrition 0.000 claims 1
- 239000003549 soybean oil Substances 0.000 claims 1
- 125000005457 triglyceride group Chemical group 0.000 claims 1
- 239000000155 melt Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006126 semicrystalline polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910001491 alkali aluminosilicate Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000012936 correction and preventive action Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011496 digital image analysis Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004790 ingeo Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Definitions
- This invention relates to organic polymer compositions that compost under ambient conditions.
- the compositions relate to polylactic acid and polylactonc blends.
- Biological derived polyesters derived from synthetic analogs such as polylactic acid and polylactones have been of interest in fields in which biocompatibility and enzymatic decomposition is desirable.
- polylactic acid and polylactones e.g., polyhydroalkoanates, “PHAs”
- PHAs polyhydroalkoanates
- lactone based polymers and copolymers have been used in the medical industry for scaffolding and the like.
- More recently, such polymers have been considered for packaging due to their compostability at ambient conditions (e.g., landfillable). These have, however, seen limited market penetration due to shortcomings such as a low deformation and degradation temperatures.
- PLA polylactic acid
- compostable deforms readily when heated to ⁇ 50 °C.
- PCL polycaprolactone
- An illustration of the invention is a composition comprising a polycaprolactone, polylactic acid, where the polylactic acid is a continuous matrix and the polycaprolactone is present as separate individual domains within the polylactic acid.
- the article may be a film, sheet or container that is useful as a food package that may be re-heated and the like.
- a further illustration is a method of forming a composition comprising, shearing polylactic acid and polycaprolactone at a weight ratio of polycaprolactone/polylactic acid of 0.67 to 0.1 at a temperature and time sufficient to form the composition of the first aspect.
- the composition is comprised of PLA and PCL where the PLA is a continuous matrix having individual domains of PCL dispersed therein.
- the PLA may be any suitable PLA such as those known in the art.
- the PLA may be any form of PLA such as those formed using L-lactide, D-lactide, or combination thereof.
- the amount of PLA or specifically L-lactide is at least 50%, 60%, 70%, 80%, 90% or 95% to 98% or 100% (100% may include trace amounts of D-lactide) by weight of the monomer used to make the PLA.
- the PLA or semicrystalline polymer may have any Mw to realize a blend with the PCLto form the composition.
- the PLA may have a weight average molecular weight (Mw) of about 10 kDa to 500 kDa.
- the melt flow rate (MFR) of the semi-crystalline polymer may be any useful to form the composition.
- the MFR of the blend of the PLA and PCL of the composition may be from 25, 50, 60 or 70 to 90, 100, 125 or 150 grams (210°C/10 min, 2.16kg).
- suitable PLAs are available under the tradename INGEO Biopolymer 6252D and 3260HP from NatureWorks LLC and LUMINY L105 from Total Corbion PLA.
- the polycaprolactone may be any suitable such as those in the art.
- the PCL may be any that realizes the composition and in particular one that realizes the desired increase in distortion temperature.
- Distortion temperature herein means the distortion temperature as determined y ASTM D-648 using a 46 MPa load.
- the polycaprolactonc generally has sufficient molecular weight so that it is a solid at room temperature ⁇ 20 °C.
- the polycaprolactone has a molecular weight of at least about 10,000 or 30,000 Da to any practicable molecular weight such as 500 kDa.
- the high molecular weight polycaprolactones illustrative may be represented by: where R 1 is hydrogen or an aromatic or a straight chain or branched aliphatic backbone, which can optionally contain one or more non-interfering substituents such as hydroxyl or amine groups, w is 1 if R 1 is hydrogen, and w otherwise has an average value of about 1 to about 4, M 1 is oxygen or — NR2 — where R2 is hydrogen or a non-interfering aromatic or aliphatic group, and the product of w times x is greater than about 175.
- the product of w times x is preferably at least about 250 and more preferably between about 250 and about 440.
- Such PCLs may be produced by known methods such as those described in U.S.
- PCL may be those available under CAS Registry No. 25248-42-4 and those under the Tradenames VIATEL from Ashland and CAPA from Perstorp.
- the amount of the PCL in the composition is an amount such that the PCL forms discrete domains within a continuous matrix of the PLA.
- the amount of PCL is from 1%, 5%, or 10% to 50%, 30% or 20% by weight of the PCL and PLA in the composition.
- the PLA may have a heat distortion temperature of about 60 °C and the composition may have a heat distortion temperature of at least 90 °C, 95 °C or 100 °C even though the PCL has a melt temperature of about 60 °C to about 65 °C.
- the domain size is sufficiently small to realize the desired microstructure leading to the improved heat distortion temperature.
- the PCL domain size may range from 1 to 10 micrometers 1 to 5 millimeters.
- the PLA and PCL are blended in a proportion such that the PCL is present in the composition as dispersed separated domains within a continuous matrix of the PLA.
- the amount of PCL is less than 50%, 40%, 30%, 25% or 20% to a sufficient amount to realize the desired properties such as at least about 1%, 2% or 5% by weight.
- the equivalent spherical diameter average domain size is about 0.1 micrometer, 0.2 micrometer, 0.5 micrometer or 1 micrometer to about 500 micrometers, 250 micrometers, 100 micrometers, 50 micrometers, 25 micrometers or 10 micrometers.
- the size may be determined by micrographic techniques such as those known in the art and may employ digital image analysis or manual techniques such as line intercept methods applied to a micrograph.
- the domains are typically spheroidal but may be any shape such as ovoid.
- the composition may be comprised of compatibilizers to facilitate the formation of the desired composition microstructure.
- the compatibilizers are ones that are approved for food contact.
- suitable compatibilizers include triglycerides including ones that have been functionalized.
- the compatibilizers may be epoxidized or saponified triglycerides such as epoxidized vegetable oils containing unsaturation (e.g., soybeen or linseed oil) and maleated vegetable oils (formation of an ester or salt of an ester using maleic acid or maleic acid anhydride).
- the compatibilizer in addition may be present to realize the desired melt flow characteristics useful for forming the desired articles made therefrom.
- the amount of compatibilizer is from about 0.01% , 0.1%, 1% to 10%, 5% or 2.5% by weight of the composition,
- the composition may contain further additives that are useful in organic polymer compositions, including but not limited to, one or more of an ultraviolet (UV) stabilizer, filler, lubricant, plasticizer, pigment, flame retardant, or solvent.
- UV ultraviolet
- the composition is essentially free of solvent (i.e., at most a trace amount, which may be at most 10 parts per million (ppm) by weight of the composition, 1 ppm).
- the amount of any particular additive may be any useful amount to realize a particular property desired in the article formed from the composition.
- the amount of the additive or additives, when present, is at most about 60%, 25%, 10% or 5% by weight of the composition.
- the composition does not have a plasticizer such as BPA (bisphenol A).
- the compostable composition may be made without using other typical polymers such as polyhydroxyalkonoates (PHAs) including polyhydroxybutyrate.
- PHAs polyhydroxyalkonoates
- the filler may be any useful filler such as those known in the art. Examples of the filler ceramics, metals, carbon (c.g., graphite, carbon black, graphene), polymeric particulates having a higher melting temperature or decomposition temperature than the PLA (e.g., crosslinked polymeric particulates, vulcanized rubber particulates and the like), plant-based fillers (e.g., wood, nutshell, grain and rice hull flours or particles).
- Exemplary fillers include calcium carbonate, talc, silica, wollastonite, clay, calcium sulfate, mica, inorganic glass (e.g., silica, alumino-silicate, borosilicate, alkali alumino silicate and the like), oxides (e.g., alumina, zirconia, magnesia, silica “quartz”, and calcia), carbides (e.g., boron carbide and silicon carbide), nitrides (e.g., silicon nitride, aluminum nitride), combinations of oxynitride, oxycarbides, or combination thereof.
- inorganic glass e.g., silica, alumino-silicate, borosilicate, alkali alumino silicate and the like
- oxides e.g., alumina, zirconia, magnesia, silica “quartz”, and calcia
- the filler comprises an acicular filler such as talc, clay minerals, chopped inorganic glass, metal, or carbon fibers, mullite, mica, wollastanite or combination thereof.
- the filler is comprised of talc, calcium carbonate, clay or combination thereof.
- the composition contains an additive that improves oxygen scavenging or reduces the permeability of oxygen.
- a metal fatty acid ester such as a metal stearate may be used (e.g., cobalt stearate, magnesium stearate, manganese stearate). Typically, these may be present in an amount in the composition from 0.1%, 0.5%, or 1% to 5%, 3% or 2%.
- the composition has an oxygen transmission of at most about 0.05, 0.01 or 0.002 mol/(m 2 -s) as determined by ASTM D1434-82 and typically may be at least about 0.0001 or 0.005.
- the composition may be made by any suitable method for blending organic polymers under shear at temperatures sufficient to realize the desired blend of the PLA and PCL.
- the agitation may be any suitable, but typically requires high shear which may be provided by known apparatus such as extruders (e.g., twin screw), banbury mixers, colloid mills, homogenizers, ultrasonic agitation and combinations thereof. In particular' it may be desirable to provide high shear by physical mixing via a twin screw extruder.
- the agitation may be provided the entire time for forming the composition, such as provided for by extrusion of the composition into pellets and the like.
- the temperature may be any in which sufficient flow of the PLA and PCL occurs for time sufficient to realize the composition. Desirably, the temperature is within 30°C or 20 °C of the melt temperature of the PLA and for a short time to reduce any decomposition or reduction of the molecular weight of the PLA and PCL. Typically, the temperature is from about 150 °C to about 200 °C and the time may be from 1 minute, 5 minutes, 10 minutes or 15 minutes to 4 hours, 3 hours, 1 hour or 0.5 hour.
- the composition may be made into articles by any suitable plastic forming method such as those known in the art including, for example, injection molding, extrusion, blow molding, cast fdm extrusion, blow molding, fiber spinning and thermoforming.
- the composition may be made into articles useful for contact with food, pharmaceuticals, and human contact such as packaging and in particular food packaging, medical devices, and pharmaceutical articles. Particular examples include food trays, plates, cups, utensils, steam baskets, microwavable food containers, syringes, tubes, pill cutters, pill counters, packaging films and the like.
- the composition’s properties may be further treated after forming the composition of the article such as a heat treatment below the melt temperature of the composition (PLA or PCL melt temperature) for a time that induces, for example further crystallization of the PLA, PCL or combination thereof.
Abstract
Polycaprolactone (PCL) and polylactic acid (PLA) are blended to form composition where the polylactic acid is a continuous matrix and the polycaprolactone is present as separate individual domains within the polylactic acid. The blends have a distortion temperature that exceeds the neat PLA distortion temperature even though the PCL has a melt temperature (~ 60 °C) at or near the neat PLA distortion temperature. The compositions may be useful for plastic articles that are compostable at ambient conditions such as those seen in landfills and backyard composters.
Description
Atty. Doc. No. JABI-203-A-WO
COMPOSTABLE COMPOSITION
TECHNICAL FIELD
[0001] This invention relates to organic polymer compositions that compost under ambient conditions. In particular, the compositions relate to polylactic acid and polylactonc blends.
BACKGROUND
[0002] Biological derived polyesters derived from synthetic analogs such as polylactic acid and polylactones (e.g., polyhydroalkoanates, “PHAs”) have been of interest in fields in which biocompatibility and enzymatic decomposition is desirable. For example, lactone based polymers and copolymers have been used in the medical industry for scaffolding and the like. [0003] More recently, such polymers have been considered for packaging due to their compostability at ambient conditions (e.g., landfillable). These have, however, seen limited market penetration due to shortcomings such as a low deformation and degradation temperatures. For example, polylactic acid (PLA) even though compostable deforms readily when heated to ~50 °C. Common polylactones such as polycaprolactone (PCL) similarly is a biodegradable polyester, but has a low melting temperature of about 60 °C. This has precluded such materials from being used as food containers that may also be useful for food preparation involving heating (e.g., boiling, steaming or microwaving).
[0004] Accordingly, it would be desirable to provide polymer packaging and containers that are biodegradable under ambient conditions (e.g., land fills or backyard composters) that may also be used to prepare food or store food typical in food preparation in the home or commercially.
SUMMARY
[0005] It has been discovered that compositions of polylactic acid (PLA) blended with polycaprolactone (PCL), where the PLA is the majority realizes surprisingly increased distortion temperatures compared to each of the polymers individually. It is particularly surprising in that the distortion temperature is increased above the melt temperature of PCL in the composition.
Without being bound or limiting in any way, it is believed that certain amount of PCL blended with the PLA may cause further crystallization of the PLA when blending, the domains of PCL within the matrix of PLA inhibit the flexibility of amorphous chains, for example, causing crystallization during heating or some other mechanism of raising the glass transition temperature or crystallinity of the PLA in the composition.
[0006] An illustration of the invention is a composition comprising a polycaprolactone, polylactic acid, where the polylactic acid is a continuous matrix and the polycaprolactone is present as separate individual domains within the polylactic acid.
[0007] Another illustration is an article comprised of the composition of the first aspect. In particular, the article may be a film, sheet or container that is useful as a food package that may be re-heated and the like.
[0008] A further illustration is a method of forming a composition comprising, shearing polylactic acid and polycaprolactone at a weight ratio of polycaprolactone/polylactic acid of 0.67 to 0.1 at a temperature and time sufficient to form the composition of the first aspect.
DETAILED DESCRIPTION
[0009] The composition is comprised of PLA and PCL where the PLA is a continuous matrix having individual domains of PCL dispersed therein. The PLA may be any suitable PLA such as those known in the art. Illustratively, the PLA may be any form of PLA such as those formed using L-lactide, D-lactide, or combination thereof. Desirably, the amount of PLA or specifically L-lactide is at least 50%, 60%, 70%, 80%, 90% or 95% to 98% or 100% (100% may include trace amounts of D-lactide) by weight of the monomer used to make the PLA.
[0010] The PLA or semicrystalline polymer may have any Mw to realize a blend with the PCLto form the composition. Typically, the PLA may have a weight average molecular weight (Mw) of about 10 kDa to 500 kDa. The melt flow rate (MFR) of the semi-crystalline polymer may be any useful to form the composition. For example, the MFR of the blend of the PLA and PCL of the composition may be from 25, 50, 60 or 70 to 90, 100, 125 or 150 grams (210°C/10 min, 2.16kg). Examples of suitable PLAs are available under the tradename INGEO Biopolymer 6252D and 3260HP from NatureWorks LLC and LUMINY L105 from Total Corbion PLA.
[0011] The polycaprolactone may be any suitable such as those in the art. For example, the PCL may be any that realizes the composition and in particular one that realizes the desired
increase in distortion temperature. Distortion temperature herein means the distortion temperature as determined y ASTM D-648 using a 46 MPa load. The polycaprolactonc generally has sufficient molecular weight so that it is a solid at room temperature ~20 °C. Generally the polycaprolactone has a molecular weight of at least about 10,000 or 30,000 Da to any practicable molecular weight such as 500 kDa. The high molecular weight polycaprolactones illustrative may be represented by:
where R1 is hydrogen or an aromatic or a straight chain or branched aliphatic backbone, which can optionally contain one or more non-interfering substituents such as hydroxyl or amine groups, w is 1 if R1 is hydrogen, and w otherwise has an average value of about 1 to about 4, M1 is oxygen or — NR2 — where R2 is hydrogen or a non-interfering aromatic or aliphatic group, and the product of w times x is greater than about 175. The product of w times x is preferably at least about 250 and more preferably between about 250 and about 440. Such PCLs may be produced by known methods such as those described in U.S. Pat. Nos. 2,890,208; 3,021,309; 3,021,317 and 3,919,163. The PCL may be those available under CAS Registry No. 25248-42-4 and those under the Tradenames VIATEL from Ashland and CAPA from Perstorp.
[0012] The amount of the PCL in the composition is an amount such that the PCL forms discrete domains within a continuous matrix of the PLA. Generally, the amount of PCL is from 1%, 5%, or 10% to 50%, 30% or 20% by weight of the PCL and PLA in the composition.
[0013] It has been surprisingly found that when the PCL is blended into the PLA sufficiently, domains of the PCL are dispersed throughout the PLA and the heat distortion temperature increases compared to the neat PLA by 20 or 30 degrees C or more. For example, the PLA may have a heat distortion temperature of about 60 °C and the composition may have a heat distortion temperature of at least 90 °C, 95 °C or 100 °C even though the PCL has a melt temperature of about 60 °C to about 65 °C.
[0014] Generally, the domain size is sufficiently small to realize the desired microstructure leading to the improved heat distortion temperature. For example, the PCL domain size may
range from 1 to 10 micrometers 1 to 5 millimeters. Generally, the PLA and PCL are blended in a proportion such that the PCL is present in the composition as dispersed separated domains within a continuous matrix of the PLA. Generally, the amount of PCL is less than 50%, 40%, 30%, 25% or 20% to a sufficient amount to realize the desired properties such as at least about 1%, 2% or 5% by weight. Desirably, the equivalent spherical diameter average domain size is about 0.1 micrometer, 0.2 micrometer, 0.5 micrometer or 1 micrometer to about 500 micrometers, 250 micrometers, 100 micrometers, 50 micrometers, 25 micrometers or 10 micrometers. The size may be determined by micrographic techniques such as those known in the art and may employ digital image analysis or manual techniques such as line intercept methods applied to a micrograph. The domains are typically spheroidal but may be any shape such as ovoid.
[0015] The composition may be comprised of compatibilizers to facilitate the formation of the desired composition microstructure. Desirably, the compatibilizers are ones that are approved for food contact. Examples of suitable compatibilizers include triglycerides including ones that have been functionalized. Illustratively, the compatibilizers may be epoxidized or saponified triglycerides such as epoxidized vegetable oils containing unsaturation (e.g., soybeen or linseed oil) and maleated vegetable oils (formation of an ester or salt of an ester using maleic acid or maleic acid anhydride). The compatibilizer in addition may be present to realize the desired melt flow characteristics useful for forming the desired articles made therefrom. Generally, the amount of compatibilizer is from about 0.01% , 0.1%, 1% to 10%, 5% or 2.5% by weight of the composition,
[0016] If desired, the composition may contain further additives that are useful in organic polymer compositions, including but not limited to, one or more of an ultraviolet (UV) stabilizer, filler, lubricant, plasticizer, pigment, flame retardant, or solvent. Desirably, the composition is essentially free of solvent (i.e., at most a trace amount, which may be at most 10 parts per million (ppm) by weight of the composition, 1 ppm). The amount of any particular additive may be any useful amount to realize a particular property desired in the article formed from the composition. Generally, the amount of the additive or additives, when present, is at most about 60%, 25%, 10% or 5% by weight of the composition. Even though a plasticizer may be present, it is desirable that the composition does not have a plasticizer such as BPA (bisphenol A). Likewise, the compostable composition may be made without using other typical polymers such as polyhydroxyalkonoates (PHAs) including polyhydroxybutyrate.
[0017] The filler may be any useful filler such as those known in the art. Examples of the filler ceramics, metals, carbon (c.g., graphite, carbon black, graphene), polymeric particulates having a higher melting temperature or decomposition temperature than the PLA (e.g., crosslinked polymeric particulates, vulcanized rubber particulates and the like), plant-based fillers (e.g., wood, nutshell, grain and rice hull flours or particles). Exemplary fillers include calcium carbonate, talc, silica, wollastonite, clay, calcium sulfate, mica, inorganic glass (e.g., silica, alumino-silicate, borosilicate, alkali alumino silicate and the like), oxides (e.g., alumina, zirconia, magnesia, silica “quartz”, and calcia), carbides (e.g., boron carbide and silicon carbide), nitrides (e.g., silicon nitride, aluminum nitride), combinations of oxynitride, oxycarbides, or combination thereof. In certain embodiments, the filler comprises an acicular filler such as talc, clay minerals, chopped inorganic glass, metal, or carbon fibers, mullite, mica, wollastanite or combination thereof. In a particular embodiment, the filler is comprised of talc, calcium carbonate, clay or combination thereof.
[0018] Desirably, the composition contains an additive that improves oxygen scavenging or reduces the permeability of oxygen. For example, a metal fatty acid ester such as a metal stearate may be used (e.g., cobalt stearate, magnesium stearate, manganese stearate). Typically, these may be present in an amount in the composition from 0.1%, 0.5%, or 1% to 5%, 3% or 2%. Desirably, the composition has an oxygen transmission of at most about 0.05, 0.01 or 0.002 mol/(m2-s) as determined by ASTM D1434-82 and typically may be at least about 0.0001 or 0.005.
[0019] The composition may be made by any suitable method for blending organic polymers under shear at temperatures sufficient to realize the desired blend of the PLA and PCL. The agitation may be any suitable, but typically requires high shear which may be provided by known apparatus such as extruders (e.g., twin screw), banbury mixers, colloid mills, homogenizers, ultrasonic agitation and combinations thereof. In particular' it may be desirable to provide high shear by physical mixing via a twin screw extruder. The agitation may be provided the entire time for forming the composition, such as provided for by extrusion of the composition into pellets and the like.
[0020] The temperature may be any in which sufficient flow of the PLA and PCL occurs for time sufficient to realize the composition. Desirably, the temperature is within 30°C or 20 °C of the melt temperature of the PLA and for a short time to reduce any decomposition or reduction of
the molecular weight of the PLA and PCL. Typically, the temperature is from about 150 °C to about 200 °C and the time may be from 1 minute, 5 minutes, 10 minutes or 15 minutes to 4 hours, 3 hours, 1 hour or 0.5 hour.
[0021] The composition may be made into articles by any suitable plastic forming method such as those known in the art including, for example, injection molding, extrusion, blow molding, cast fdm extrusion, blow molding, fiber spinning and thermoforming. The composition may be made into articles useful for contact with food, pharmaceuticals, and human contact such as packaging and in particular food packaging, medical devices, and pharmaceutical articles. Particular examples include food trays, plates, cups, utensils, steam baskets, microwavable food containers, syringes, tubes, pill cutters, pill counters, packaging films and the like. The composition’s properties may be further treated after forming the composition of the article such as a heat treatment below the melt temperature of the composition (PLA or PCL melt temperature) for a time that induces, for example further crystallization of the PLA, PCL or combination thereof.
Claims
1. A composition comprising a polycaprolactone and polylactic acid, where the poly lactic acid is a continuous matrix and the polycaprolactone is present as separate individual domains within the poly lactic acid.
2. The composition of claim 1 , wherein the polylactic acid is present in an amount from 60% to 95% by weight of the polylactic acid and polycaprolactone present in the composition.
3. The composition of claim 2, wherein the polycaprolactone is present in an amount of 10% to 50% by weight of the polylactic acid and polycaprolactone present in the composition.
4. The composition of any one of the preceding claims, wherein the composition further comprises a compatibilizer.
5. The composition of claim 4, wherein the compatibilizer is a triglyceride.
6. The composition of claim 5, wherein the triglyceride is a functionalized triglyceride.
7. The composition of claim 5, wherein the triglyceride is a saponified or epoxidized vegetable oil.
8. The composition of claim 7, wherein the triglyceride is epoxidized soybean oil.
9. The composition of any one of the preceding claims wherein the composition is comprised of a filler.
10. The composition of claim 9, wherein the filler is comprised of one or more of metal oxide, metal carbonate, and metal hydroxide.
11 . The composition of claim 10, wherein the filler is comprised of one or more of calcium carbonate and a clay.
12. The composition of any one of the preceding claims, wherein the composition is comprised of an amount of filler and an amount compatibilizer.
13. The composition of claim 12, wherein the amount of filler is from 10% to 60% by weight of the composition and the amount of compatibilizer is 0.01% to 10% by weight of the composition.
14. The composition of any one of the preceding claims wherein the composition is further comprised of an oxygen scavenger.
15. The composition of claim 14, wherein the oxygen scavenger is comprised of a metal fatty acid salt.
16. The composition of claim 15, wherein the metal fatty acid salt is an oleate, stearate or mixture thereof.
17. The composition of claim 16, wherein the metal fatty acid salt is cobalt stearate, magnesium stearate, manganese stearate or combination thereof.
18. An article comprised of the composition of any one of the preceding claims.
19. The article of claim 18, wherein the article has a heat deflection temperature of at least 90 °C
20. The article of claim 19, wherein the article has a heat deflection temperature of at least 100 °C.
21 . The article of any one of claims 18 to 20, wherein the composition of the article has an oxygen transmission rate of at most 0.05 mol/(m2-s).
22. The article of any one of claims 18 to 21, wherein the article is a food package.
23. A composition comprising a polycaprolactone, poly lactic acid, blended together at a ratio polycaprolactone/poly lactic acid of 0.01 to 0.67 by weight.
24. The composition of claim 23, wherein the ratio is 0.1 to 0.4.
25. The composition of either claim 23 or 24, wherein the heat distortion temperature exceeds the heat distortion temperature of the polylactic acid in the absence of the polycaprolactone.
26. The composition of any one of claims 23 to 25, wherein the heat distortion temperature is at least 90 °C.
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