AU2013203994A1 - Bio-based polyethylene terephthalate polymer and method of making the same - Google Patents
Bio-based polyethylene terephthalate polymer and method of making the same Download PDFInfo
- Publication number
- AU2013203994A1 AU2013203994A1 AU2013203994A AU2013203994A AU2013203994A1 AU 2013203994 A1 AU2013203994 A1 AU 2013203994A1 AU 2013203994 A AU2013203994 A AU 2013203994A AU 2013203994 A AU2013203994 A AU 2013203994A AU 2013203994 A1 AU2013203994 A1 AU 2013203994A1
- Authority
- AU
- Australia
- Prior art keywords
- bio
- weight percent
- component
- polyethylene terephthalate
- based material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 59
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 59
- 229920000642 polymer Polymers 0.000 title claims abstract description 38
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 58
- 150000002009 diols Chemical class 0.000 claims abstract description 37
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims abstract description 35
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000000346 sugar Nutrition 0.000 claims description 12
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 11
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 241000196324 Embryophyta Species 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 240000008042 Zea mays Species 0.000 claims description 7
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 7
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 7
- 235000005822 corn Nutrition 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 235000020971 citrus fruits Nutrition 0.000 claims description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 6
- 150000003505 terpenes Chemical class 0.000 claims description 6
- 235000007586 terpenes Nutrition 0.000 claims description 6
- 235000016068 Berberis vulgaris Nutrition 0.000 claims description 5
- 241000335053 Beta vulgaris Species 0.000 claims description 5
- 240000000111 Saccharum officinarum Species 0.000 claims description 5
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 5
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 5
- 244000061456 Solanum tuberosum Species 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229930006737 car-3-ene Natural products 0.000 claims description 4
- 229930007796 carene Natural products 0.000 claims description 4
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 claims description 4
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- 235000001510 limonene Nutrition 0.000 claims description 4
- 229940087305 limonene Drugs 0.000 claims description 4
- 239000010773 plant oil Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical compound [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 230000000153 supplemental effect Effects 0.000 claims description 2
- 229930007927 cymene Natural products 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 6
- 229920000747 poly(lactic acid) Polymers 0.000 description 5
- XCYJPXQACVEIOS-UHFFFAOYSA-N 1-isopropyl-3-methylbenzene Chemical compound CC(C)C1=CC=CC(C)=C1 XCYJPXQACVEIOS-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005567 liquid scintillation counting Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- XVHIUKSUZLPFCP-UHFFFAOYSA-N 2-(hydroxymethyl)benzaldehyde Chemical compound OCC1=CC=CC=C1C=O XVHIUKSUZLPFCP-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 208000003643 Callosities Diseases 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 101100003989 Neosartorya fumigata (strain ATCC MYA-4609 / Af293 / CBS 101355 / FGSC A1100) atrI gene Proteins 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 241000283984 Rodentia Species 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- HUMHYXGDUOGHTG-HEZXSMHISA-N alpha-D-GalpNAc-(1->3)-[alpha-L-Fucp-(1->2)]-D-Galp Chemical compound O[C@H]1[C@H](O)[C@H](O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](O[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](O)[C@@H](CO)OC1O HUMHYXGDUOGHTG-HEZXSMHISA-N 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920006025 bioresin Polymers 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010103 injection stretch blow moulding Methods 0.000 description 1
- AIHDCSAXVMAMJH-GFBKWZILSA-N levan Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(CO[C@@H]2[C@H]([C@H](O)[C@@](O)(CO)O2)O)O1 AIHDCSAXVMAMJH-GFBKWZILSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 101150041594 soti gene Proteins 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- CHBNMKPHUSAEJE-UHFFFAOYSA-N terpinene group Chemical group C12=C(C(CC(C1(C)C)C2)C2(C(=C1C(C(C2)C1)(C)C)C)C1C(=C2C(C(C1)C2)(C)C)C)C CHBNMKPHUSAEJE-UHFFFAOYSA-N 0.000 description 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
A bio-based polyethylene terephthalate polymer comprising from about 25 to about 75 weight percent of a terephthalate component and from about 20 to about 50 weight percent of 5 a diol component, wherein at least about one weight percent of at least one of the terephthalate and/or the diol component is derived from at least one bio-based material. A method of producing a bio-based polyethylene terephthalate polymer comprising obtaining a diol component comprising ethylene glycol, obtaining a terephthalate component comprising terephthalic acid, wherein at least one of the diol component and/or the diol component is 10 derived from at least one bio-based material, and reacting the diol component and the terephthalate component to form a bio-based polyethylene terephthalate polymer comprising from about 25 to about 75 weight percent of the terephthalate component and from about 20 to about 50 weight percent of the diol component.
Description
1 Bio-based Polyethylene Terephthalate Polymer and Method of Making the Same The present application is a divisional application from Australian patent 5 application number 2009229151, the entire disclosure of which is incorporated herein by reference. RE.LAI D APPiLICAiTON DATA [o1ll The present application Claims priory un&de 35 UAC. 119(e) 1 US Prvisionaf Application Number 614049, entitd "Bio-based Polyethylene Terephthaate and Articles Mkade from Bionsed PolyetLene TerephthAaat anid fikd on March 28, 2008, FIELD OF INVENTION t002] This ivenion reltes gncrally to a bio-basd polyehlene tepthaat polymerthat contains a terephthalate and/or a dii component that derives pardally or totally from bio-hased materials. BACKGaROUND P00t3| Polyethylene terephthalate and it copyesters (hCr'einafter refened to ckHectively as "PET" or "yethyln tcrepthfalat") is a widely used raw atrI alfr uAing pamkaging articles in part due w their excellent IXCmbinatiOn of clarity, mchlnicat and gas barirpropet's, Exarnples of PIET products include. but are not limited to., bottles and containes for pakging fod prducs, soft drInks, alcoholic beverages, detergents, cosmtics, pharmaceuica products and edibk oils. [1004] Most commeciaI methods produce Ptt with petrochemica1y derived raw materials, Therefore, te Cost of tproduiaol is closely ded to the prIce of petroleuM, P h - i PET conribues to gttnh use missions due to its high pttkoletm derived carbon content. Furthermort petrochemicals take hundreds af thousands of y t o fSona naturally, rmaing ptochmicallerived products non renewahle whicb mTIrs *y cannot I en-made, re-gron, or regeneraed at a rato comparatfiveto its cosumpton, 2 [0051 One approach to subsiating perochmicallyskriv PET IhS bcen the pmducion of polylactic acid (PLA) bokplastics fm1 bio-hased materials such. a cow , ice, or otr suar and staShprodcing plant\ ee eag. U S Pat, No. 6,%9J99 A dcscibed in US, Pat. No,. ,409,7$1 ad S, Pat App. No. 200701 S7876, ataempts havo been made to use PLA resins in injection strech molding pcses for producing containers. 1owxever, jitis o0e.n di fficuh to adap PLA into urgentt PET producion .ines or to satisfacsorily substitute PEP with PLA in many applications due to the significanty different properdes between PLA and PE1 For example, PLAtypieally has a lower gas barier property than PET, which makes PLA onUtainers les suitable for storing items such s carbonated beverages or beverag rsesitive to oxygen, Furthenrore, most recycling systems currently in use are designed for PET which would be contaminated if PLA was introduced. This problem could be overcome by costly soits 5 schas uing distincive bottk types between PLA and;4 PE or b vesting in suitable soti ng technology or new reytvlig strdsP ja'6 Thus, there exis a need fr a PET derived from renewahlk eouces that shrs similar properties as pereum-derved PE. it woldd be also desirable in some applications if the PET derived from renewabl resources can be processed through exising PET numfaeturing facilities and/or can be readily reeyeed through the systems designed for relying peroeum--derived PET. [0007] Other aspects, features, and advantages of this invention will be apparent from the following detailed description, drawings and claims. 5 [0007A] The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application. 10 [0007B] Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification (including the claims) they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not precluding the presence of one or more other features, integers, steps or components, or group thereof.
2a BlUIF DESCRIPTION OF THE DRAWING [im6 Fig, I is a flowchart illustration of the mthod f making a bioased polyethylene terephthalate prodhict that patialy or totaihy deives from bio-based materials, DETAILED DESCRIPTION( OF THE PRESENT INVENTION (W9 T he term Tbio-,ased," as used in this application, indiates the inclusion of some Compo*nt that dedvs from" at least one bio-baseJ material, FOr example, a" based PET pmlymtr" would be a PET pNolmer that compsles at Ieasoe co" ) mpento I that partially or totally denves from at least one bio-based mateaL Bio-Based PET Polymer [O01 One emibodimanit of the present invention *ncompasses a biobased PET polymer that comprises fom about 25 to about 75 weight percent of a tercphthalatc component and fr about 20 to about 50 weight percent of a diol component. wherein at WO 2009/120457 PCT/US2009/035849 3 least about one weight percent of at least one of the terephthalate component and/or the diol component is derived from at least one bio-based material. In a more particular embodiment, at least about 20 weight percent of at least one of the terephthalate 70 component and/or the diol component is derived from at least one bio-based material. [0011] In one embodiment, the bio-based PET polymer comprises from about 30 to about 70 weight percent of the terephthalate component. In a more particular embodiment, the bio-based PET polymer comprises from about 40 to about 65 weight percent of the terephthalate component. In another embodiment, the bio-based PET 75 polymer comprises from about 25 to about 45 weight percent of the diol component. In a more particular embodiment, the bio-based PET polymer comprises from about 25 to about 35 weight percent of the diol component. [0012] According to a particular embodiment of the invention, the terephthalate component is selected from terephthalic acid, dimethyl terephthalate, isophthalic acid, and 80 a combination thereof In a more particular embodiment, at least about ten weight percent of the terephthalate component is derived from at least one bio-based material. In one embodiment, the terephthalate component comprises at least about 70 weight percent of terephthalic acid. In a more particular embodiment, at least about one weight percent., preferably at least about ten weight percent, of the terephthalic acid is made from at least 85 one bio-based material. [00131 In another embodiment, the diol component is selected from ethylene glycol, cyclohexane dimethanol, and a combination thereof In a more particular embodiment, the diol component comprises at least about one weight percent of cyclohexane dimethanol. In another embodiment, at least about ten weight percent of the 90 diol component is derived from at least one bio-based material. [00141 Other ingredients may be added to the bio-based PET polymer. Those of ordinary skill in the art would readily be able to select the suitable ingredient(s) to add to the bio-based PET polymer to improve the desired properties, which may depend on the type of application intended. In a particular embodiment, the bio-based PET polymer may 95 further comprise a supplemental component selected from at least one coloring agent, at least one fast reheat additive, at least one gas barrier additive, at least one UV blocking additive, and a combination thereof [0015] Bio-based PET polymers may be used to form bio-based resins, which may be further processed into bio-based containers using methods including, but not limited to, WO 2009/120457 PCT/US2009/035849 4 100 injection molding and stretch blow molding. Embodiments of the present invention encompass bio-based containers that comprise the bio-based PET polymers of the above described embodiments. To be suitable for certain applications, containers have a certain intrinsic viscosity to withstand movements, shelving, and other requirements. In a more particular embodiment of the present invention, the bio-based container has an intrinsic 105 viscosity from about GA5 dL/g to about 1.0 dL/g. 10016] It is known in the art that carbon-14 (C-14), which has a half life of about 5,700 years, is found in bio-based materials but not in fossil fuels. Thus, "bio-based materials" refer to organic materials in which the carbon comes from non-fossil biological sources. Examples of bio-based materials include, but are not limited to, sugars, starches, 110 corns, natural fibers, sugarcanes, beets, citrus fruits, woody plants, cellulosics, lignocelluosics, hemicelluloses, potatoes, plant oils, other polysaccharides such as pectin, chitin, levan, and pullulan, and a combination thereof According to a particular embodiment, the at least one bio-based material is selected from corn, sugarcane, beet, potato, starch, citrus fruit, woody plant, cellulosic lignin, plant oil, natural fiber, oily wood 115 feedstock, and a combination thereof [0017] As explained previously, the detection of C-14 is indicative of a bio-based material. C-14 levels can be determined by measuring its decay process (disintegrations per minute per gram carbon or dpngC) through liquid scintillation counting. In one embodiment of the present invention, the bio-based PET polymer comprises at least about 120 0.1 dpm/gC (disintegrations per minute per grain carbon) of C-14. [00181 The invention is further illustrated by the following example, which is not to be construed in any way as imposing limitations on the scope thereof On the contrary, it is to be clearly understood that resort may be had to various other embodiments, modifications, and equivalents thereof which, after reading the description herein, may 125 suggestion themselves to those skilled in the art without departing from the spirit of the present invention and/or scope of the appended claims. Example J [0019] The following samples were measured, in a blind test fashion, to determine 130 the presence of C-14 content by liquid scintillation counting. The levels detected were normalized to existing data available at University of Georgia that correlates the C-14 level to the bio-based percentage. The results are shown in Table 1.
WO 2009/120457 PCT/US2009/035849 5 Table I Sample {Sample Description C-14 % bio-hased ID (dpm/gC) material I Ethylene glycol (totally derived from ethanol 15 i 0.13 100 i1 converted from sugars) 2 Ethylene glycol (totally derived from corn) 15 + 0.13 98 + 1 3 Ethylene glycol (totally derived from petroleum) 0.04 i 0.13 0+1 4 Ethylene glycol (totally derived from petroleum) 0.04 0.13 0 1 5 PET (totally derived from petroleum) 0.07 0.13 0 1 6 PET (contains about 30 wt% of ethylene glycol 3,01 1013 21 11 from sample I and about 70 wt% of terephthalic acid derived from petroleum) 135 As shown in Table 1, samples totally derived from petroleum (samples 2 3 and 4) contain a negligible amount of C-14, indicating that about zero percent of the sample is made from bio-based materials. In contrast, samples that contain materials known to be partially or totally derived from a bio-based material (corn or sugar) show a much higher level of C 140 14. Based on the data, about 0.14 dpm/gC corresponds to about one percent of bio-based material in the sample. Method of Making Polyethylene Terephthalate Polymer WO 2009/120457 PCT/US2009/035849 6 [0020] Referring to Fig. 1, embodiments of the present invention also encompass a 145 process for producing a bio-based PET polymer 16 comprising obtaining a diol component 12 comprising ethylene glycol 12a [step 20], obtaining a terephthalate component 14 comprising terephthalic acid [step 22], wherein at least about one weight percent of one of the diol component and/or the terephthalate component (12, 14) is derived from at least GOOH COOCH2CH 2 OH: +2HOcH 2
CH
2 0H --- nH22-- - - (- C2C OH COOH COOCH 2
CH
2 OH + (n-1)HOCH2CH 2 OH one bio-based material 10, reacting the diol component 12 and the terephthalate 150 component 14 to form a bio-based PET polymer 16 [step 24], wherein the bio-based PET polymer 16 comprises from about 25 to about 75 weight percent of the terephthalate component 14 and from about 20 to about 50 weight percent of the diol component 12. In a more particular embodiment, as illustrated in Reaction I, step 24 further comprises reacting the diol component 12 and the terephthalate component 14 through an 155 esterification reaction to form bio-based PET monomers 16a, which then undergo polymerization to form the bio-based PET polymer 16. Reaction I [0021] In a particular embodiment, at least about one weight percent of the diol component 12 is derived from at least one bio-based material 10. In a more particular 160 embodiment, at least ten weight percent of the diol component 12 is derived from at least one bio-based material 10. In still a more particular embodiment, at least 30 weight percent of the diol component 12 is derived from at least one bio-based material 10. [0022] The diol component 12 may be partially or totally derived from at least one bo-based material using any process. In one embodiment, step 20 comprises obtaining a 165 sugar or derivatives thereof from at least one bio-based material and fermenting the sugar or derivatives thereof to ethanol. In another embodiment, step 20 comprises gasification of at least one bio-based material 10 to produce syngas, which is converted to ethanol. In a more particular embodiment, as illustrated by Reaction II, step 20 further comprises dehydrating ethanol to ethylene, oxidizing ethylene to ethylene oxide, and converting 170 ethylene oxide to ethylene glycol.
WO 2009/120457 PCT/US2009/035849 7
H
2 0
CH
3
CH
2 OH - C HCH 2 - H 2
C$CH
2 - HOCH 2
CH
2 OH
H
2 0 Reaction 11 In another embodiment, step 20 comprises obtaining a sugar or derivatives thereof from at least one bio-based material and converting the sugar or derivatives thereof to a mixture 175 comprising ethylene glycol and at least one glycol excluding the ethylene glycol. Step 20 further comprises isolating the ethylene glycol from the mixture. The mixture may be repeatedly reacted to obtain higher yields of ethylene glycol. In a more particular embodiment, the at least one glycol is selected from butanediols, propandiols, and glycerols. 180 [0023] According to another embodiment, at least about one weight percent of the terephthalate component 14 is derived from at least one bio-based material 10. In a more particular embodiment, at least ten weight percent of the terephthalate component 14 is derived from at least one bio-based material 10. In still a more particular embodiment, at least 30 weight percent of the terephthalate component 14 is derived from at least one bio 185 based material 10. [00241 The terephthalate component 14 may be partially or totally derived from at least one bio-based material using any process. In one embodiment, as illustrated in Reaction III, step 22 comprises extracting carene from an oily wood feedstock, converting the carene to p-cymene and m-cymene by dehyodrgenation and aromatization, and 190 oxidizing p-cymene and m-cymene to terephthalic acid and isophthalic acid.
-
_ HO -7 --- -r - x - . 0 H O W Reaction III In another embodiment, as illustrated in Reaction IV, step 22 comprises extracting limonene from at least one bio-based material, converting the limonene to at least one terpene, converting the terpene to p-cymene and oxiding the p-cymene to terephthalic acid. In a more particular embodiment, the at least one terpene is selected from terpinene, 195 dipentene, terpinolene, and combinations thereof. In still a more particular embodiment, WO 2009/120457 PCT/US2009/035849 8 the at least one bio-based material is selected from a citrus fruit, a woody plant, or a combination thereof. 0 Terpene(s) - [- --- H 0 Reaction IV 200 [0025] In one embodiment of the present invention, as described in Reaction V, step 22 comprises extracting hydroxymethylifurfural from a bio-based material, converting hydroxynethylfirfiral to a first intermediate, reacting the first intermediate with ethylene to form a second intermediate, treating the second intermediate with an acid in the presence of a catalyst to form hydroxymethyl benzaldehyde, and oxidizing hydroxymethyl 205 benzaldehyde to terephthalic acid. In a more particular embodiment, the hydroxymethylfurfural is extracted from a bio-based material selected from corn syrup, sugars, cellulose, and a combination thereof In still a more particular embodiment, the ethylene is derived from at least one bio-based material. 00 0O DE.> H H H HOHDV OH OH 0 Reaction V In another embodiment, step 22 comprises gasification of at least one bio-based material 210 10 to produce syngas, converting syngas p-xylene, and oxidizing p-xylene in acid to form terephthalic acid. [0026] In one embodiment, at least about one weight percent of the terephthalate component 14 is derived from at least one bio-based material 10 and at least about one weight percent of the diol component 12 is derived from at least one bio-based material 215 10. In a more particular embodiment, at least about 25 weight percent of the terephthalate WO 2009/120457 PCT/US2009/035849 9 component 14 is derived from at least one bio-based material 10. In still a more particular embodiment, at least about 70 weight percent of the diol component 12 is derived from at least one bio-based material 10. According to a particular embodiment, the bio-based material is selected from corn, sugarcane, beet, potato, starch, citrus fruit, woody plant, 220 cellulosic lignin, plant oil, natural fiber, oily wood feedstock, and a combination thereof. 10027) In another embodiment, the method further comprises making a bio-based PET product 18 ftom the bio-based PET polymer 16. The bio-based PET product 18 may be used in various applications, including, but not limited to, as a beverage container. In another embodiment, the bio-based PET product 18 may be recycled or reused through 225 recycling systems [step 26] designed for petroleum-derived PET products. 100281 It should be understood that the foregoing relates to particular embodiments of the present invention, and that numerous changes may be made therein without departing from the scope of the invention as defined from the following claims. 230
Claims (17)
1. A bio-based polyethylene terephthalate polymer comprising from about 25 to about 75 weight percent of a terephthalate component, 235 wherein the terephthalate component is selected from terephthalic acid, dimethyl terephthalate, isophthalic acid, and a combination thereof; and from about 20 to about 50 weight percent of a diol component, wherein the diol component is selected from ethylene glycol, cyclohexane dimethanol, and a combination thereof; 240 wherein at least about one weight percent of at least one of the terephthalate and/or the diol component is derived from at least one bio-based material.
2. The bio-based polyethylene terephthalate polymer of claim 1. wherein at least about ten weight percent of the diol component is derived from at least one bio 245 based material.
3. The bio-based polyethylene terephthalate polymer of claims 1-2, wherein at least about ten weight percent of the terephthalate component is derived from at least one bio-based material. 250
4. The bio-based polyethylene terephthalate polymer of claims 1-2, wherein the terephthalate component comprises at least about 70 weight percent of terephthalie acid and wherein at least about ten weight percent of the terephthalic acid is derived from at least one bio-based material. 255
5. The bio-based polyethylene terephthalate polymer of claims 1-4, wherein the at least one bio-based material is selected from corn, sugarcane, beet, potato, starch, citrus fruit, woody plant, cellulosic lignin, plant oil, natural fiber, oily wood feedstock, and a combination thereof 260
6. The bio-based polyethylene terephthalate polymer of claims 1-5, further comprising a supplemental component selected from at least one coloring agent, at least one fast reheat resistant additive, at least one gas barrier additive, at least one UV blocking additive, and a combination thereof. WO 2009/120457 PCT/US2009/035849 11 265
7. A bio-based container comprising the bio-based polyethylene terephthalate polymer of claims 1-6.
8. The bio-based container of claim 7, wherein the bio-based polyethylene terephthalate polymer comprises at least about 0.1 dpnr/gC of carbon-14. 270
9. A bio-based container comprising a bio-based polyethylene terephthalate polymer, wherein at least one weight percent of the polyethylene terephthalate polymer is derived from at least one bio-based material, wherein the bio-based container has an intrinsic viscosity from about 0.45 dL/g to about 1.0 dL/g.
10. The bio-based container of claim 9, wherein the bio-based polyethylene terephthalate polymer comprises from about 25 to about 75 weight percent of a terephthalate component, wherein the terephthalate component is selected from terephthaiic acid, dimethyl terephthalate, isophthalic acid, and a combination 280 thereof; and from about 20 to about 50 weight percent of a diol component, wherein the diol component is selected from ethylene glycol, cyclohexane dimethanol, and a combination thereof; wherein at least about ten weight percent of the diol component is derived 285 from at least one bio-based material. I1. A method of producing a bio-based polyethylene terephthalate polymer comprising a. obtaining a diol component comprising ethylene glycol; b. obtaining a terephthalate component comprising terephthalic acid, 290 wherein at least one of the diol and/or the terephthalate component is derived from at least one bio-based material; and c. reacting the diol component and the terephthalate component to form a bio based polyethylene terephthalate polymer, wherein the bio-based polyethylene terephthalate polymer comprises from about 25 to about 75 295 weight percent of the terephthalate component and from about 20 to about 50 weight percent of the diol component.
WO 2009/120457 PCT/US2009!035849 12
12. The method of claims 11, wherein the at least one bio-based material is selected 300 from com, sugarcane, beet, potato, starch, citrus fruit, woody plant, cellulosic lignin, oily wood feedstock, and a combination thereof.
13. The method of claims 11-12, wherein step (a) further comprises i. obtaining sugar or derivatives thereof from at least one bio-based 305 material; ii. fermenting sugar or derivatives thereof to ethanol; iii. dehydrating ethanol to ethylene; iv. oxidizing ethylene to ethylene oxide; and v. converting ethylene oxide to ethylene glycol. 310
14. The method of claims 11-12, wherein step (a) further comprises i. obtaining sugar or derivatives thereof from at least one bio-based material; ii. reacting sugar or derivatives to form a mixture comprising ethylene 315 glycol and at least one glycol excluding the ethylene glycol; and iii. separating ethylene glycol from the mixture.
15. The method of claims 11-14, wherein step (b) further comprises i. obtaining carene from at least one bio-based material; 320 ii. converting carene to cymene; and iii. oxidizing cymene to terephthalic acid.
16. The method of claims 11-14, wherein step (b) further comprises i. obtaining limonene from at least one bio-based material; 325 ii. converting the limonene to at least one terpene; iii. converting the at least one terpene to cymene; and iv. oxidizing cynene to terephthalic acid.
17. The bio -based polyethylene terephthalate polymer produced b y the method of 330 claims 11-16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2013203994A AU2013203994A1 (en) | 2008-03-28 | 2013-04-11 | Bio-based polyethylene terephthalate polymer and method of making the same |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61/040,349 | 2008-03-28 | ||
| US12/210,208 | 2008-09-14 | ||
| AU2009229151A AU2009229151A1 (en) | 2008-03-28 | 2009-03-03 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2013203994A AU2013203994A1 (en) | 2008-03-28 | 2013-04-11 | Bio-based polyethylene terephthalate polymer and method of making the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2009229151A Division AU2009229151A1 (en) | 2008-03-28 | 2009-03-03 | Bio-based polyethylene terephthalate polymer and method of making the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2013203994A1 true AU2013203994A1 (en) | 2013-05-02 |
Family
ID=48446833
Family Applications (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2013203994A Abandoned AU2013203994A1 (en) | 2008-03-28 | 2013-04-11 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2015201282A Abandoned AU2015201282A1 (en) | 2008-03-28 | 2015-03-11 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2017200475A Abandoned AU2017200475A1 (en) | 2008-03-28 | 2017-01-24 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2018282376A Active AU2018282376B2 (en) | 2008-03-28 | 2018-12-20 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2021203661A Abandoned AU2021203661A1 (en) | 2008-03-28 | 2021-06-04 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2023208135A Pending AU2023208135A1 (en) | 2008-03-28 | 2023-07-26 | Bio-based polyethylene terephthalate polymer and method of making the same |
Family Applications After (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2015201282A Abandoned AU2015201282A1 (en) | 2008-03-28 | 2015-03-11 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2017200475A Abandoned AU2017200475A1 (en) | 2008-03-28 | 2017-01-24 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2018282376A Active AU2018282376B2 (en) | 2008-03-28 | 2018-12-20 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2021203661A Abandoned AU2021203661A1 (en) | 2008-03-28 | 2021-06-04 | Bio-based polyethylene terephthalate polymer and method of making the same |
| AU2023208135A Pending AU2023208135A1 (en) | 2008-03-28 | 2023-07-26 | Bio-based polyethylene terephthalate polymer and method of making the same |
Country Status (1)
| Country | Link |
|---|---|
| AU (6) | AU2013203994A1 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482586A (en) * | 1982-09-07 | 1984-11-13 | The Goodyear Tire & Rubber Company | Multi-layer polyisophthalate and polyterephthalate articles and process therefor |
| GB9013481D0 (en) * | 1990-06-15 | 1990-08-08 | Ici Plc | Polyester polymer products |
| US6500890B2 (en) * | 2000-12-15 | 2002-12-31 | Wellman, Inc. | Polyester bottle resins having reduced frictional properties and methods for making the same |
| US7479517B2 (en) * | 2003-11-28 | 2009-01-20 | Futura Polyesters Ltd. | Process for the preparation of fast reheat (FRH) bottle grade polyethyleneterephthalate (PET) resin |
| JP4380654B2 (en) * | 2005-04-22 | 2009-12-09 | 三菱化学株式会社 | Polyester and method for producing the same |
| JP2007176873A (en) * | 2005-12-28 | 2007-07-12 | Toray Ind Inc | Production method for raw material of resin, and resin and its production method |
| US20080103340A1 (en) * | 2006-10-27 | 2008-05-01 | Archer-Daniels-Midland Company | Applications of biobased glycol compositions |
| US7385081B1 (en) * | 2007-11-14 | 2008-06-10 | Bp Corporation North America Inc. | Terephthalic acid composition and process for the production thereof |
-
2013
- 2013-04-11 AU AU2013203994A patent/AU2013203994A1/en not_active Abandoned
-
2015
- 2015-03-11 AU AU2015201282A patent/AU2015201282A1/en not_active Abandoned
-
2017
- 2017-01-24 AU AU2017200475A patent/AU2017200475A1/en not_active Abandoned
-
2018
- 2018-12-20 AU AU2018282376A patent/AU2018282376B2/en active Active
-
2021
- 2021-06-04 AU AU2021203661A patent/AU2021203661A1/en not_active Abandoned
-
2023
- 2023-07-26 AU AU2023208135A patent/AU2023208135A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU2021203661A1 (en) | 2021-07-01 |
| AU2015201282A1 (en) | 2015-04-02 |
| AU2018282376B2 (en) | 2021-03-04 |
| AU2023208135A1 (en) | 2023-08-17 |
| AU2017200475A1 (en) | 2017-02-09 |
| AU2018282376A1 (en) | 2019-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7051917B2 (en) | Bio-based polyethylene terephthalate polymer and its preparation method | |
| US20190194388A1 (en) | Bio-based polyethylene terephthalate packaging and method of making thereof | |
| CA2754220C (en) | Bio-based polyethylene terephthalate packaging and method of making thereof | |
| AU2023206170A1 (en) | Bio-based polyethylene terephthalate packaging and method of making thereof | |
| AU2018282376B2 (en) | Bio-based polyethylene terephthalate polymer and method of making the same | |
| HK1154257A (en) | Bio-based polyethylene terephthalate polymer and method of making the same | |
| CA3035396C (en) | Process for producing a bio-based polyethylene terephthalate (pet) polymer, entirely from bio-based materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK5 | Application lapsed section 142(2)(e) - patent request and compl. specification not accepted |