NZ623391B2 - Monolayer carbon dioxide barrier pet bottles - Google Patents
Monolayer carbon dioxide barrier pet bottles Download PDFInfo
- Publication number
- NZ623391B2 NZ623391B2 NZ623391A NZ62339112A NZ623391B2 NZ 623391 B2 NZ623391 B2 NZ 623391B2 NZ 623391 A NZ623391 A NZ 623391A NZ 62339112 A NZ62339112 A NZ 62339112A NZ 623391 B2 NZ623391 B2 NZ 623391B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- linear
- branched
- alkyl
- aryl
- chosen
- Prior art date
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- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 14
- 239000001569 carbon dioxide Substances 0.000 title abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 109
- -1 isoquinoline compound Chemical class 0.000 claims abstract description 89
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 229920000642 polymer Polymers 0.000 claims abstract description 54
- 229920005601 base polymer Polymers 0.000 claims abstract description 43
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 41
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 41
- 229920000728 polyester Polymers 0.000 claims abstract description 10
- 239000004743 Polypropylene Substances 0.000 claims abstract description 3
- 229920001155 polypropylene Polymers 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 117
- 125000003118 aryl group Chemical group 0.000 claims description 82
- 229910052760 oxygen Inorganic materials 0.000 claims description 82
- 239000001301 oxygen Substances 0.000 claims description 78
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 78
- 229910052739 hydrogen Inorganic materials 0.000 claims description 70
- 125000000217 alkyl group Chemical group 0.000 claims description 65
- 239000001257 hydrogen Substances 0.000 claims description 63
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 48
- 239000002516 radical scavenger Substances 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 125000001072 heteroaryl group Chemical group 0.000 claims description 39
- 125000000623 heterocyclic group Chemical group 0.000 claims description 37
- 150000002431 hydrogen Chemical group 0.000 claims description 33
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 32
- 125000005842 heteroatoms Chemical group 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 239000011593 sulfur Substances 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 16
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- 125000005275 alkylenearyl group Chemical group 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 125000000304 alkynyl group Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- QGJHNXPHHOCUAH-UHFFFAOYSA-N 2,3-dihydrobenzo[de]isoquinolin-1-one Chemical compound C1=CC(C(=O)NC2)=C3C2=CC=CC3=C1 QGJHNXPHHOCUAH-UHFFFAOYSA-N 0.000 claims description 3
- UKOVZLWSUZKTRL-UHFFFAOYSA-N Naphthalid Chemical compound C1=CC(C(=O)OC2)=C3C2=CC=CC3=C1 UKOVZLWSUZKTRL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 3
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 3
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 4
- CNNBIMYYNFIICO-UHFFFAOYSA-N naphthalene-1,8-dicarboxamide Chemical compound C1=CC(C(N)=O)=C2C(C(=O)N)=CC=CC2=C1 CNNBIMYYNFIICO-UHFFFAOYSA-N 0.000 claims 2
- 235000012174 carbonated soft drink Nutrition 0.000 abstract description 8
- 238000004806 packaging method and process Methods 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 3
- KYNSBQPICQTCGU-UHFFFAOYSA-N benzopyran Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 11
- 125000004429 atoms Chemical group 0.000 description 9
- 235000013405 beer Nutrition 0.000 description 9
- 125000002837 carbocyclic group Chemical group 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 230000002000 scavenging Effects 0.000 description 7
- 150000002148 esters Chemical group 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 238000010128 melt processing Methods 0.000 description 6
- 230000001603 reducing Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 235000013361 beverage Nutrition 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004614 Process Aid Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- 235000014171 carbonated beverage Nutrition 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 102100017978 MNT Human genes 0.000 description 3
- 101700073680 MNT Proteins 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000004698 Polyethylene (PE) Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910004682 ON-OFF Inorganic materials 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000005218 alkyleneheteroaryl group Chemical group 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbamate Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000001186 cumulative Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 2
- 238000001998 small-angle neutron scattering Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (-)-propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-IGMARMGPSA-N (12)6C Chemical compound [12C] OKTJSMMVPCPJKN-IGMARMGPSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- 125000004607 1,2,3,4-tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 description 1
- JHJOAXHWIIFJJU-UHFFFAOYSA-N 1,2-difluoroethane Chemical group F[CH]CF JHJOAXHWIIFJJU-UHFFFAOYSA-N 0.000 description 1
- XBJHZEUYCYYCLK-UHFFFAOYSA-N 1,2-dimethylidenecyclopentane Chemical group C=C1CCCC1=C XBJHZEUYCYYCLK-UHFFFAOYSA-N 0.000 description 1
- 150000000185 1,3-diols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N 1,6-Hexanediol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- ZYGCUMLAHDLONP-UHFFFAOYSA-N 1-(2-oxopiperidin-3-yl)piperidin-2-one Chemical compound O=C1NCCCC1N1C(=O)CCCC1 ZYGCUMLAHDLONP-UHFFFAOYSA-N 0.000 description 1
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N 2,3-Butanediol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- LPAGFVYQRIESJQ-UHFFFAOYSA-N 2,3-dihydro-1H-indole Chemical compound C1=CC=C2NCCC2=C1 LPAGFVYQRIESJQ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- 125000003974 3-carbamimidamidopropyl group Chemical group C(N)(=N)NCCC* 0.000 description 1
- 125000004176 4-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1F)C([H])([H])* 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BJUPTJXRJDXLHF-UHFFFAOYSA-N 6,7-dihydro-5H-cyclopenta[d]pyrimidine Chemical compound N1=CN=C2CCCC2=C1 BJUPTJXRJDXLHF-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- RMRFFCXPLWYOOY-UHFFFAOYSA-N Allyl radical Chemical group [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 description 1
- PZKKGVMGEQCWSC-UHFFFAOYSA-N C1(=CC=CC2=CC=CC(=C12)CC(=O)N)CC(=O)N Chemical group C1(=CC=CC2=CC=CC(=C12)CC(=O)N)CC(=O)N PZKKGVMGEQCWSC-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N Dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N Dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000035695 Efflux Effects 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 210000003800 Pharynx Anatomy 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- 229960004063 Propylene glycol Drugs 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N Triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 229940088594 Vitamin Drugs 0.000 description 1
- 238000000333 X-ray scattering Methods 0.000 description 1
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005418 aryl aryl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000005841 biaryl group Chemical group 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- BVCRERJDOOBZOH-UHFFFAOYSA-N bicyclo[2.2.1]heptanyl Chemical group C1C[C+]2CC[C-]1C2 BVCRERJDOOBZOH-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005043 dihydropyranyl group Chemical group O1C(CCC=C1)* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229920000578 graft polymer Polymers 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000005969 isothiazolinyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000003971 isoxazolinyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 235000009808 lpulo Nutrition 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000009448 modified atmosphere packaging Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 239000002365 multiple layer Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 125000000160 oxazolidinyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 125000005646 oximino group Chemical group 0.000 description 1
- 125000004430 oxygen atoms Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000000135 prohibitive Effects 0.000 description 1
- 230000001737 promoting Effects 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004001 thioalkyl group Chemical group 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 238000000214 vapour pressure osmometry Methods 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229930003231 vitamins Natural products 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N β-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
Disclosed herein is a polymer composition comprising a base polymer and a chromene or isoquinoline compound b), wherein the base polymer is a polymer such as polyester, polyethylene terephthalate (PET), or polypropylene, and the substituents of compound b) are as defined in the specification. Also discloses is the use of the polymer composition in an article that can provide a barrier to carbon dioxide diffusion. The disclosed polymer compositions and articles can be utilized in packaging to retard or prevent the diffusion of carbon dioxide out of a carbonated liquid such as a carbonated soft drink. iscloses is the use of the polymer composition in an article that can provide a barrier to carbon dioxide diffusion. The disclosed polymer compositions and articles can be utilized in packaging to retard or prevent the diffusion of carbon dioxide out of a carbonated liquid such as a carbonated soft drink.
Description
MONOLAYER CARBON DIOXIDE BARRIER PET BOTTLES
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of priority to U.S. Provisional Application No.
61/533,449, filed September 12, 2011, which is hereby incorporated by reference in its
entirety.
BACKGROUND
Carbon dioxide comprising beverages (carbonated beverages), inter alia, soda pop,
beer, and the like, provide an organoleptic property that results in a “refreshing mouth-feel”
when consumed. Carbonated beverages, especially carbonated soft drinks, must retain their
carbonation in order to not be perceived as “flat.” Carbonated beverages that are packed in
polyethylene terephthalate (PET) comprising containers can lose their amount of
carbonation due to diffusion of carbon dioxide through the PET container.
Current solutions to solving the problem of CO diffusion include providing a
thicker container, however, this solution leads to an increased cost in the manufacturing of
the container. Another solution is to provide a non-permeable barrier, for example, a resin.
The added cost of the resin, as the modification of the equipment and processes for
manufacturing PET contains makes this solution cost prohibitive. The addition of certain
adjuncts, i.e., MXD6, would have an impact on the clarity and optical properties of the
resulting PET polymer comprising container.
Therefore, there is a need for providing increased shelf life for carbonated beverages
that does not involve increasing the thickness of the container walls, applying an expensive
coating, admixing ingredients that impact container clarity, or any combination to these
limitations. It is an object of the present invention to go some way to meeting this need,
and/or to at least provide the public with a useful choice.
[0004a] In this specification where reference has been made to patent specifications, other
external documents, or other sources of information, this is generally for the purpose of
providing a context for discussing the features of the invention. Unless specifically stated
otherwise, reference to such external documents is not to be construed as an admission that
such documents, or such sources of information, in any jurisdiction, are prior art, or form
part of the common general knowledge in the art.
SUMMARY
Disclosed herein are polymer compositions, comprising:
a) a base polymer;
b) from about 0.1% to about 10% by weight of a compound having the formula:
wherein R to R are each independently chosen from:
i) hydrogen;
ii) C -C substituted or unsubstituted linear, branched, or cyclic alkyl;
1 12
iii) C -C substituted or unsubstituted linear, branched, or cyclic
2 12
alkenyl;
iv) C -C substituted or unsubstituted linear or branched alkynyl;
2 12
v) C or C substituted or unsubstituted aryl;
6 10
vi) C -C substituted or unsubstituted heterocyclic;
vii) C -C substituted or unsubstituted heteroaryl;
1 11
10a 10b 11
viii) –[C(R )(R )] OR ;
wherein R is chosen from:
a) –H;
b) C -C substituted or unsubstituted linear, branched, or cyclic
1 12
alkyl or C -C substituted or unsubstituted linear, branched,
1 12
or cyclic haloalkyl;
c) C or C substituted or unsubstituted aryl or C -C
6 10 7 20
alkylenearyl;
d) C -C substituted or unsubstituted heterocyclic; and
e) C -C substituted or unsubstituted heteroaryl;
1 11
10a 10b 12a 12b
ix) –[C(R )(R )] N(R )(R );
12a 12b
wherein R and R are each independently chosen from:
a) –H;
b) –OR ;
R is hydrogen or C -C4 linear alkyl;
c) C -C substituted or unsubstituted linear, branched, or cyclic
1 12
alkyl;
d) C or C substituted or unsubstituted aryl;
6 10
e) C -C substituted or unsubstituted heterocyclic;
f) C -C substituted or unsubstituted heteroaryl; and
1 11
12a 12b
g) R and R can be taken together to form a substituted or
unsubstituted ring having from 3 to 10 carbon atoms and from
0 to 3 heteroatoms chosen from oxygen, nitrogen, and sulfur;
10a 10b 14
x) –[C(R )(R )]yC(O)R ;
wherein R is chosen from:
a) C -C substituted or unsubstituted linear, branched, or cyclic
1 12
alkyl;
b) –OR ;
wherein R is hydrogen, substituted or unsubstituted C -C
linear alkyl, C or C substituted or unsubstituted aryl, C -C
6 10 1 9
substituted or unsubstituted heterocyclic, C -C substituted or
1 11
unsubstituted heteroaryl; and
16a 16b
c) –N(R )(R );
16a 16b
wherein R and R are each independently hydrogen, C -
C substituted or unsubstituted linear, branched, or cyclic
alkyl; C or C substituted or unsubstituted aryl; C -C
6 10 1 9
substituted or unsubstituted heterocyclic; C -C substituted or
1 11
16a 16b
unsubstituted heteroaryl; or R and R can be taken
together to form a substituted or unsubstituted ring having
from 3 to 10 carbon atoms and from 0 to 3 heteroatoms
chosen from oxygen, nitrogen, and sulfur;
10a 10b 17
xi) –[C(R )(R )] OC(O)R ;
wherein R is chosen from:
a) C -C substituted or unsubstituted linear, branched, or cyclic
1 12
alkyl; and
18a 18b
b) –N(R )(R );
18a 18b
R and R are each independently hydrogen, C -C
1 12
substituted or unsubstituted linear, branched, or cyclic alkyl;
C or C substituted or unsubstituted aryl; C -C substituted
6 10 1 9
or unsubstituted heterocyclic; C -C substituted or
1 11
18a 18b
unsubstituted heteroaryl; or R and R can be taken
together to form a substituted or unsubstituted ring having
from 3 to 10 carbon atoms and from 0 to 3 heteroatoms
chosen from oxygen, nitrogen, and sulfur;
10a 10b 19 20
xii) –[C(R )(R )] NR C(O)R ;
wherein R is chosen from:
a) –H; and
b) C1-C4 substituted or unsubstituted linear, branched, or cyclic
alkyl;
wherein R is chosen from:
a) C -C substituted or unsubstituted linear, branched, or cyclic
1 12
alkyl; and
21a 21b
b) –N(R )(R );
21a 21b
R and R are each independently hydrogen, C -C
1 12
substituted or unsubstituted linear, branched, or cyclic alkyl;
C or C substituted or unsubstituted aryl; C -C substituted
6 10 1 9
or unsubstituted heterocyclic; C -C substituted or
1 11
21a 21b
unsubstituted heteroaryl; or R and R can be taken
together to form a substituted or unsubstituted ring having
from 3 to 10 carbon atoms and from 0 to 3 heteroatoms
chosen from oxygen, nitrogen, and sulfur;
10a 10b
xiii) –[C(R )(R )] CN;
10a 10b
xiv) –[C(R )(R )] NO ;
10a 10b 22
xv) –[C(R )(R )] SO R ;
R is hydrogen, hydroxyl, substituted or unsubstituted C -C linear
or branched alkyl; substituted or unsubstituted C , C , or C aryl;
6 10 14
C -C alkylenearyl; C -C substituted or unsubstituted heterocyclic;
7 15 1 9
or C -C substituted or unsubstituted heteroaryl; and
1 11
xvi) halogen;
10a 10b
xvii) –[C(R )(R )] (CH X ) CH X ; wherein X is halogen, the index j
y j’ k’ h j k
is an integer from 0 to 2, the index k is an integer from 1 to 3, j + k =
3; the index j’ is an integer from 0 to 2, the index k’ is and integer
from 0 to 2, j’ + k’ = 2; the index h is from 0 to 5;
10a 10b
R and R are each independently hydrogen or C -C alkyl; and
the index y is from 0 to 5;
R and R can be taken together to from a 5 to 7 member ring containing from 3 to 7
carbon atoms and from 0 to 2 heteroatoms chosen from oxygen, sulfur, or nitrogen, wherein
one or more of the carbon atoms can be substituted, unsubstituted, or a carbonyl unit.
Also disclosed herein are methods of making the compositions, articles comprising
the compositions, and methods of making the articles.
[0006a] In a first aspect, the present invention provides a polymer composition, comprising:
a) a base polymer; and
b) from about 0.1% to about 10% by weight of a compound having the formula:
wherein R and R are each independently chosen from:
i) C -C linear, branched, or cyclic alkyl;
1 12
ii) C -C linear, branched, or cyclic alkenyl;
2 12
iii) C -C linear or branched alkynyl;
2 12
iv) C or C aryl;
6 10
10a 10b 11
v) –[C(R )(R )] OR ;
wherein R is chosen from:
a) –H;
b) C -C linear, branched, or cyclic alkyl or C -C linear,
1 12 1 12
branched, or cyclic haloalkyl; and
c) C or C aryl or C -C alkylenearyl;
6 10 7 20
10a 10b 12a 12b
vi) –[C(R )(R )] N(R )(R );
12a 12b
wherein R and R are each independently chosen from:
a) –H;
b) –OR ;
R is hydrogen or C -C linear alkyl;
c) C -C linear, branched, or cyclic alkyl; and
1 12
d) C or C aryl;
6 10
10a 10b 14
vii) –[C(R )(R )] C(O)R ;
wherein R is chosen from:
a) C -C linear, branched, or cyclic alkyl;
1 12
b) –OR ;
wherein R is hydrogen, C -C linear alkyl, or C or C aryl;
1 4 6 10
16a 16b
c) –N(R )(R );
16a 16b
wherein R and R are each independently hydrogen, C -
C linear, branched, or cyclic alkyl; or C or C aryl;
12 6 10
10a 10b 17
viii) –[C(R )(R )]yOC(O)R ;
wherein R is chosen from:
a) C -C linear, branched, or cyclic alkyl; and
1 12
18a 18b
b) –N(R )(R );
18a 18b
R and R are each independently hydrogen, C -C linear,
1 12
branched, or cyclic alkyl; or C or C aryl;
6 10
10a 10b 19 20
ix) –[C(R )(R )] NR C(O)R ;
wherein R is chosen from:
a) –H; and
b) C -C linear, branched, or cyclic alkyl;
wherein R is chosen from:
a) C -C linear, branched, or cyclic alkyl; and
1 12
21a 21b
b) –N(R )(R );
21a 21b
R and R are each independently hydrogen, C -C linear,
1 12
branched, or cyclic alkyl; or C or C aryl;
6 10
10a 10b
x) –[C(R )(R )] CN;
10a 10b
xi) –[C(R )(R )] NO ;
10a 10b 22
xii) –[C(R )(R )] SO R ;
R is hydrogen, hydroxyl, C -C linear or branched alkyl; C , C , or
1 4 6 10
C aryl; C -C alkylenearyl; C -C heterocyclic; or C -C
14 7 15 1 9 1 11
heteroaryl; and
xiii) halogen;
10a 10b
xiv) –[C(R )(R )] (CH X ) CH X ; wherein X is halogen, the index j
y j’ k’ h j k
is an integer from 0 to 2, the index k is an integer from 1 to 3, j + k =
3; the index j’ is an integer from 0 to 2, the index k’ is and integer
from 0 to 2, j’ + k’ = 2; the index h is from 0 to 5;
10a 10b
R and R are each independently hydrogen or C -C alkyl; and
the index y is from 0 to 5;
R and R can be taken together to form a 6 member ring containing from 4
to 6 carbon atoms and from 0 to 2 heteroatoms chosen from oxygen, sulfur,
or nitrogen, wherein one or more of the carbon atoms can be a carbonyl unit;
wherein R to R are each hydrogen.
[0006b] In a further aspect, the present invention provides a preform comprising the
composition according to the first aspect.
[0006c] In another aspect, the present invention provides an article of manufacture
comprising the composition according to the first aspect.
[0006d] In another aspect, the present invention provides an article of manufacture,
comprising:
a) a base polymer;
b) from about 0.1% to about 10% by weight of a compound having the formula:
wherein R and R are each independently chosen from:
i) C -C linear, branched, or cyclic alkyl;
1 12
ii) C -C linear, branched, or cyclic alkenyl;
2 12
iii) C -C linear or branched alkynyl;
2 12
iv) C or C aryl;
6 10
10a 10b 11
v) –[C(R )(R )] OR ;
wherein R is chosen from:
a) –H;
b) C -C linear, branched, or cyclic alkyl or C -C linear,
1 12 1 12
branched, or cyclic haloalkyl;
c) C or C aryl or C -C alkylenearyl;
6 10 7 20
10a 10b 12a 12b
vi) –[C(R )(R )] N(R )(R );
12a 12b
wherein R and R are each independently chosen from:
a) –H;
b) –OR ;
R is hydrogen or C -C4 linear alkyl;
c) C -C linear, branched, or cyclic alkyl;
1 12
d) C or C aryl;
6 10
10a 10b 14
vii) –[C(R )(R )] C(O)R ;
wherein R is chosen from:
a) C -C linear, branched, or cyclic alkyl;
1 12
b) –OR ;
wherein R is hydrogen, C1-C4 linear alkyl, or C6 or C10 aryl;
16a 16b
c) –N(R )(R );
16a 16b
wherein R and R are each independently hydrogen, C -
C linear, branched, or cyclic alkyl; or C or C aryl;
12 6 10
10a 10b 17
viii) –[C(R )(R )] OC(O)R ;
wherein R is chosen from:
a) C -C linear, branched, or cyclic alkyl; and
1 12
18a 18b
b) –N(R )(R );
18a 18b
R and R are each independently hydrogen, C -C linear,
1 12
branched, or cyclic alkyl; or C or C aryl;
6 10
10a 10b 19 20
ix) –[C(R )(R )] NR C(O)R ;
wherein R is chosen from:
a) –H; and
b) C -C linear, branched, or cyclic alkyl;
wherein R is chosen from:
a) C -C linear, branched, or cyclic alkyl; and
1 12
21a 21b
b) –N(R )(R );
21a 21b
R and R are each independently hydrogen, C -C linear,
1 12
branched, or cyclic alkyl; or C or C aryl;
6 10
10a 10b
x) –[C(R )(R )] CN;
10a 10b
xi) –[C(R )(R )] NO ;
10a 10b 22
xii) –[C(R )(R )] SO R ;
R is hydrogen, hydroxyl, C -C linear or branched alkyl; C , C , or
1 4 6 10
C aryl; C -C alkylenearyl; C -C heterocyclic; or C -C
14 7 15 1 9 1 11
heteroaryl; and
xiii) halogen;
10a 10b
xiv) –[C(R )(R )] (CH X ) CH X ; wherein X is halogen, the index j
y j’ k’ h j k
is an integer from 0 to 2, the index k is an integer from 1 to 3, j + k =
3; the index j’ is an integer from 0 to 2, the index k’ is and integer
from 0 to 2, j’ + k’ = 2; the index h is from 0 to 5;
10a 10b
R and R are each independently hydrogen or C -C alkyl; and
the index y is from 0 to 5;
R and R can be taken together to form a 6 member ring containing from 4
to 6 carbon atoms and from 0 to 2 heteroatoms chosen from oxygen, sulfur,
or nitrogen, wherein one or more of the carbon atoms can be a carbonyl unit;
wherein R to R are each hydrogen.
Additional advantages of the invention will be set forth in part in the description
which follows, and in part will be obvious from the description, or can be learned by
practice of the invention. The advantages of the invention will be realized and attained by
means of the elements and combinations particularly pointed out in the appended claims. It
is to be understood that both the foregoing general description and the following detailed
description are exemplary and explanatory only and are not restrictive of the invention, as
claimed.
[0007a] In the description in this specification reference may be made to subject matter
which is not within the scope of the appended claims. That subject matter should be readily
identifiable by a person skilled in the art and may assist in putting into practice the
invention as defined in the appended claims.
BRIEF DESCRIPTION OF THE FIGURES
The accompanying figures, which are incorporated in and constitute a part of this
specification, illustrate several aspects and together with the description serve to explain the
principles of the invention.
Figure 1 shows representative CO loss data for the disclosed polymer compositions
as described below in Example 1.
Figure 2(a) shows representative CO loss data for the disclosed polymer
compositions as described below in Example 1.
Figure 2(b) shows representative CO loss data for the disclosed polymer
compositions as described below in Example 1.
Figure 3(a) shows representative CO loss data for the disclosed polymer
compositions as described below in Example 1.
Figure 3(b) shows representative CO loss data for the disclosed polymer
compositions as described below in Example 1.
Figure 4 shows representative CO loss data for the disclosed polymer compositions
as described below in Example 2.
Figure 5 shows representative CO loss data for the disclosed polymer compositions
as described below in Example 2.
DETAILED DESCRIPTION
The present invention can be understood more readily by reference to the following
detailed description of the invention and the Examples included therein.
Before the present compounds, compositions, articles, systems, devices, and/or
methods are disclosed and described, it is to be understood that they are not limited to
specific synthetic methods unless otherwise specified, or to particular reagents unless
otherwise specified, as such can, of course, vary. It is also to be understood that the
terminology used herein is for the purpose of describing particular aspects only and is not
intended to be limiting. Although any methods and materials similar or equivalent to those
described herein can be used in the practice or testing of the present invention, example
methods and materials are now described.
Unless defined otherwise, all technical and scientific terms used herein have the
same meaning as commonly understood by one of ordinary skill in the art to which this
invention belongs. Although any methods and materials similar or equivalent to those
described herein can be used in the practice or testing of the present invention, example
methods and materials are now described.
In this specification and in the claims that follow, reference will be made to a
number of terms, which shall be defined to have the following meanings:
All percentages, ratios and proportions herein are by weight, unless otherwise
specified. All temperatures are in degrees Celsius (°C) unless otherwise specified.
Throughout the description and claims of this specification the word “comprise” and
other forms of the word, such as “comprising” and “comprises,” means including but not
limited to, and is not intended to exclude, for example, other additives, components,
integers, or steps.
As used in the description and the appended claims, the singular forms “a,” “an,”
and “the” include plural referents unless the context clearly dictates otherwise. Thus, for
example, reference to “a composition” includes mixtures of two or more such compositions,
reference to “a phenylsulfamic acid” includes mixtures of two or more such phenylsulfamic
acids, reference to “the compound” includes mixtures of two or more such compounds, and
the like.
“Optional” or “optionally” means that the subsequently described event or
circumstance can or cannot occur, and that the description includes instances where the
event or circumstance occurs and instances where it does not.
Ranges can be expressed herein as from “about” one particular value, and/or to
“about” another particular value. When such a range is expressed, another aspect includes
from the one particular value and/or to the other particular value. Similarly, when values
are expressed as approximations, by use of the antecedent “about,” it will be understood that
the particular value forms another aspect. It will be further understood that the endpoints of
each of the ranges are significant both in relation to the other endpoint, and independently
of the other endpoint. It is also understood that there are a number of values disclosed
herein, and that each value is also herein disclosed as “about” that particular value in
addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is
also disclosed. It is also understood that when a value is disclosed, then “less than or equal
to” the value, “greater than or equal to the value,” and possible ranges between values are
also disclosed, as appropriately understood by the skilled artisan. For example, if the value
“10” is disclosed, then “less than or equal to 10” as well as “greater than or equal to 10” is
also disclosed. It is also understood that throughout the application data are provided in a
number of different formats and that this data represent endpoints and starting points and
ranges for any combination of the data points. For example, if a particular data point “10”
and a particular data point “15” are disclosed, it is understood that greater than, greater than
or equal to, less than, less than or equal to, and equal to 10 and 15 are considered disclosed
as well as between 10 and 15. It is also understood that each unit between two particular
units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are
also disclosed.
As used herein, the term “substantially” means that the subsequently described event
or circumstance completely occurs or that the subsequently described event or circumstance
generally, typically, or approximately occurs. For example, when the specification
discloses that substantially all of an agent is released, a person skilled in the relevant art
would readily understand that the agent need not be completely released. Rather, this term
conveys to a person skilled in the relevant art that the agent need only be released to an
extent that an effective amount is no longer unreleased.
As used herein, the term “polymer” refers to a relatively high molecular weight
organic compound, natural or synthetic, whose structure can be represented by a repeated
small unit, the monomer (e.g., polyethylene, rubber, cellulose). Synthetic polymers are
typically formed by addition or condensation polymerization of monomers.
As used herein, the term “copolymer” refers to a polymer formed from two or more
different repeating units (monomer residues). By way of example and without limitation, a
copolymer can be an alternating copolymer, a random copolymer, a block copolymer, or a
graft copolymer. It is also contemplated that, in certain aspects, various block segments of a
block copolymer can themselves comprise copolymers.
As used herein, the term “oligomer” refers to a relatively low molecular weight
polymer in which the number of repeating units is between two and ten, for example, from
two to eight, from two to six, or form two to four. In one aspect, a collection of oligomers
can have an average number of repeating units of from about two to about ten, for example,
from about two to about eight, from about two to about six, or form about two to about four.
As used herein, the term “star polymer” refers to a branched polymer molecule in
which a single branch point gives rise to multiple linear chains or arms. The single branch
point can be a single chemical moiety or can be a highly crosslinked section of polymer. In
one aspect, a star polymer can be generally spherical in shape. In a further aspect, a star
polymer can be particle shaped. If the arms are identical the star polymer molecule is said
to be regular. If adjacent arms are composed of different repeating subunits, the star
polymer molecule is said to be variegated.
As used herein, the term “molecular weight” (MW) refers to the mass of one
molecule of that substance, relative to the unified atomic mass unit u (equal to 1/12 the
mass of one atom of carbon-12).
As used herein, the term “number average molecular weight” (M ) refers to the
common, mean, average of the molecular weights of the individual polymers. M can be
determined by measuring the molecular weight of n polymer molecules, summing the
weights, and dividing by n. M is calculated by:
wherein N is the number of molecules of molecular weight M . The number average
molecular weight of a polymer can be determined by gel permeation chromatography,
viscometry (Mark-Houwink equation), light scattering, analytical ultracentrifugation, vapor
pressure osmometry, end-group titration, and colligative properties.
As used herein, the term “weight average molecular weight” (M ) refers to an
alternative measure of the molecular weight of a polymer. M is calculated by:
wherein N is the number of molecules of molecular weight M . Intuitively, if the weight
average molecular weight is w, and a random monomer is selected, then the polymer it
belongs to will have a weight of w on average. The weight average molecular weight can
be determined by light scattering, small angle neutron scattering (SANS), X-ray scattering,
and sedimentation velocity.
As used herein, the terms “polydispersity” and “polydispersity index” (PDI) refer to
the ratio of the weight average to the number average (M /M ).
As used herein, the term “compatibilizing agent” refers to a small molecule or
polymer that has both polar and non-polar functional groups. For example, a fatty-acid ester
has both polar and non-polar functional groups.
A weight percent (wt. %) of a component, unless specifically stated to the contrary,
is based on the total weight of the formulation or composition in which the component is
included.
As used herein, nomenclature for compounds, including organic compounds, can be
given using common names, IUPAC, IUBMB, or CAS recommendations for nomenclature.
When one or more stereochemical features are present, Cahn-Ingold-Prelog rules for
stereochemistry can be employed to designate stereochemical priority, E/Z specification,
and the like. One of skill in the art can readily ascertain the structure of a compound if given
a name, either by systemic reduction of the compound structure using naming conventions,
or by commercially available software, such as CHEMDRAW (Cambridgesoft
Corporation, U.S.A.).
The following chemical hierarchy is used throughout the specification to describe
and enable the scope of the present disclosure and to particularly point out and distinctly
claim the units which comprise the compounds of the present disclosure, however, unless
otherwise specifically defined, the terms used herein are the same as those of the artisan of
ordinary skill. The term “hydrocarbyl” stands for any carbon atom-based unit (organic
molecule), said units optionally containing one or more organic functional group, including
inorganic atom comprising salts, inter alia, carboxylate salts, quaternary ammonium salts.
Within the broad meaning of the term “hydrocarbyl” are the classes “acyclic hydrocarbyl”
and “cyclic hydrocarbyl” which terms are used to divide hydrocarbyl units into cyclic and
non-cyclic classes.
As it relates to the following definitions, “cyclic hydrocarbyl” units can comprise
only carbon atoms in the ring (i.e., carbocyclic and aryl rings) or can comprise one or more
heteroatoms in the ring (i.e., heterocyclic and heteroaryl rings). For “carbocyclic” rings the
lowest number of carbon atoms in a ring are 3 carbon atoms; cyclopropyl. For “aryl” rings
the lowest number of carbon atoms in a ring are 6 carbon atoms; phenyl. For “heterocyclic”
rings the lowest number of carbon atoms in a ring is 1 carbon atom; diazirinyl. Ethylene
oxide comprises 2 carbon atoms and is a C heterocycle. For “heteroaryl” rings the lowest
number of carbon atoms in a ring is 1 carbon atom; 1,2,3,4-tetrazolyl. The following is a
non-limiting description of the terms “acyclic hydrocarbyl” and “cyclic hydrocarbyl” as
used herein.
A. Substituted and unsubstituted acyclic hydrocarbyl:
For the purposes of the present disclosure the term “substituted and unsubstituted
acyclic hydrocarbyl” encompasses 3 categories of units:
1) linear or branched alkyl, non-limiting examples of which include, methyl (C ), ethyl
(C ), n-propyl (C ), iso-propyl (C ), n-butyl (C ), sec-butyl (C ), iso-butyl (C ), tert-
2 3 3 4 4 4
butyl (C ), and the like; substituted linear or branched alkyl, non-limiting examples
of which includes, hydroxymethyl (C ), chloromethyl (C ), trifluoromethyl (C ),
1 1 1
aminomethyl (C ), 1-chloroethyl (C ), 2-hydroxyethyl (C ), 1,2-difluoroethyl (C ),
1 2 2 2
3-carboxypropyl (C ), and the like.
2) linear or branched alkenyl, non-limiting examples of which include, ethenyl (C2), 3-
propenyl (C ), 1-propenyl (also 2-methylethenyl) (C ), isopropenyl (also 2-
methylethenyl) (C ), butenyl (C ), and the like; substituted linear or branched
alkenyl, non-limiting examples of which include, 2-chloroethenyl (also 2-
chlorovinyl) (C ), 4-hydroxybutenyl (C ), 7-hydroxymethyloctenyl (C ),
2 4 9
7-hydroxymethyloct-3,5-dienyl (C ), and the like.
3) linear or branched alkynyl, non-limiting examples of which include, ethynyl (C ),
propynyl (also propargyl) (C ), propynyl (C ), and 2-methyl-hexynyl
(C ); substituted linear or branched alkynyl, non-limiting examples of which
include, 5-hydroxymethylhexynyl (C ), 6-hydroxymethylheptynyl
(C ), 5-hydroxyethylheptynyl (C ), and the like.
B. Substituted and unsubstituted cyclic hydrocarbyl:
For the purposes of the present disclosure the term “substituted and unsubstituted
cyclic hydrocarbyl” encompasses 5 categories of units:
1) The term “carbocyclic” is defined herein as “encompassing rings comprising from 3
to 20 carbon atoms, wherein the atoms which comprise said rings are limited to
carbon atoms, and further each ring can be independently substituted with one or
more moieties capable of replacing one or more hydrogen atoms.” The following
are non-limiting examples of “substituted and unsubstituted carbocyclic rings”
which encompass the following categories of units:
i) carbocyclic rings having a single substituted or unsubstituted hydrocarbon
ring, non-limiting examples of which include, cyclopropyl (C ), 2-methyl-
cyclopropyl (C ), cyclopropenyl (C ), cyclobutyl (C ), 2,3-dihydroxycyclobutyl
3 3 4
(C ), cyclobutenyl (C ), cyclopentyl (C ), cyclopentenyl (C ), cyclopentadienyl
4 4 5 5
(C ), cyclohexyl (C ), cyclohexenyl (C ), cycloheptyl (C ), cyclooctanyl (C ), 2,5-
6 6 7 8
dimethylcyclopentyl (C ), 3,5-dichlorocyclohexyl (C ), 4-hydroxycyclohexyl (C ),
6 6
and 3,3,5-trimethylcyclohexyl (C ).
ii) carbocyclic rings having two or more substituted or unsubstituted fused
hydrocarbon rings, non-limiting examples of which include, octahydropentalenyl
(C ), octahydro-1H-indenyl (C ), 3a,4,5,6,7,7a-hexahydro-3H-indenyl (C ),
8 9 9
decahydroazulenyl (C ).
iii) carbocyclic rings which are substituted or unsubstituted bicyclic hydrocarbon
rings, non-limiting examples of which include, bicyclo-[2.1.1]hexanyl,
bicyclo[2.2.1]heptanyl, bicyclo[3.1.1]heptanyl, 1,3-dimethyl[2.2.1]heptanyl,
bicyclo[2.2.2]octanyl, and bicyclo[3.3.3]undecanyl.
2) The term “aryl” is defined herein as “units encompassing at least one phenyl or
naphthyl ring and wherein there are no heteroaryl or heterocyclic rings fused to the
phenyl or naphthyl ring and further each ring can be independently substituted with
one or more moieties capable of replacing one or more hydrogen atoms.” The
following are non-limiting examples of “substituted and unsubstituted aryl rings”
which encompass the following categories of units:
i) C or C substituted or unsubstituted aryl rings; phenyl and naphthyl rings
6 10
whether substituted or unsubstituted, non-limiting examples of which include,
phenyl (C ), naphthylenyl (C ), naphthylenyl (C ), 4-fluorophenyl (C ), 2-
6 10 10 6
hydroxyphenyl (C ), 3-methylphenyl (C ), 2-aminofluorophenyl (C ), 2-(N,N-
6 6 6
diethylamino)phenyl (C ), 2-cyanophenyl (C ), 2,6-di-tert-butylphenyl (C ), 3-
6 6 6
methoxyphenyl (C ), 8-hydroxynaphthylenyl (C ), 4,5-dimethoxynaphthylen
6 10
yl (C ), and 6-cyano-naphthylenyl (C ).
10
ii) C or C aryl rings fused with 1 or 2 saturated rings to afford C -C ring
6 10 8 20
systems, non-limiting examples of which include, bicyclo[4.2.0]octa-1,3,5-trienyl
(C ), and indanyl (C ).
3) The terms “heterocyclic” and/or “heterocycle” are defined herein as “units
comprising one or more rings having from 3 to 20 atoms wherein at least one atom
in at least one ring is a heteroatom chosen from nitrogen (N), oxygen (O), or sulfur
(S), or mixtures of N, O, and S, and wherein further the ring which contains the
heteroatom is also not an aromatic ring.” The following are non-limiting examples
of “substituted and unsubstituted heterocyclic rings” which encompass the following
categories of units:
i) heterocyclic units having a single ring containing one or more heteroatoms,
non-limiting examples of which include, diazirinyl (C ), aziridinyl (C ), urazolyl
(C ), azetidinyl (C ), pyrazolidinyl (C ), imidazolidinyl (C ), oxazolidinyl (C ),
2 3 3 3 3
isoxazolinyl (C ), thiazolidinyl (C ), isothiazolinyl (C ), oxathiazolidinonyl (C ),
3 3 3 3
oxazolidinonyl (C ), hydantoinyl (C ), tetrahydrofuranyl (C ), pyrrolidinyl (C ),
3 3 4 4
morpholinyl (C ), piperazinyl (C ), piperidinyl (C ), dihydropyranyl (C ),
4 4 4 5
tetrahydropyranyl (C ), piperidinonyl (valerolactam) (C ), 2,3,4,5-tetrahydro-1H-
azepinyl (C ), 2,3-dihydro-1H-indole (C ), and 1,2,3,4-tetrahydroquinoline (C ).
6 8 9
ii) heterocyclic units having 2 or more rings one of which is a heterocyclic ring,
non-limiting examples of which include hexahydro-1H-pyrrolizinyl (C7),
3a,4,5,6,7,7a-hexahydro-1H-benzo[d]imidazolyl (C ), 3a,4,5,6,7,7a-hexahydro-1H-
indolyl (C ), 1,2,3,4-tetrahydroquinolinyl (C ), and decahydro-1H-
cycloocta[b]pyrrolyl (C ).
4) The term “heteroaryl” is defined herein as “encompassing one or more rings
comprising from 5 to 20 atoms wherein at least one atom in at least one ring is a
heteroatom chosen from nitrogen (N), oxygen (O), or sulfur (S), or mixtures of N,
O, and S, and wherein further at least one of the rings which comprises a heteroatom
is an aromatic ring.” The following are non-limiting examples of “substituted and
unsubstituted heterocyclic rings” which encompass the following categories of units:
i) heteroaryl rings containing a single ring, non-limiting examples of which
include, 1,2,3,4-tetrazolyl (C ), [1,2,3]triazolyl (C ), [1,2,4]triazolyl (C ), triazinyl
1 2 2
(C ), thiazolyl (C ), 1H-imidazolyl (C ), oxazolyl (C ), isoxazolyl (C ), isothiazolyl
3 3 3 3 3
(C ), furanyl (C ), thiophenyl (C ), pyrimidinyl (C ), 2-phenylpyrimidinyl (C ),
3 4 4 4 4
pyridinyl (C ), 3-methylpyridinyl (C ), and 4-dimethylaminopyridinyl (C )
5 5
ii) heteroaryl rings containing 2 or more fused rings one of which is a heteroaryl
ring, non-limiting examples of which include: 7H-purinyl (C ), 9H-purinyl (C ), 6-
amino-9H-purinyl (C ), 5H-pyrrolo[3,2-d]pyrimidinyl (C ), 7H-pyrrolo[2,3-
d]pyrimidinyl (C ), pyrido[2,3-d]pyrimidinyl (C ), 2-phenylbenzo[d]thiazolyl (C ),
6 7 7
1H-indolyl (C ), 4,5,6,7-tetrahydroH-indolyl (C ), quinoxalinyl (C ), 5-
8 8 8
methylquinoxalinyl (C ), quinazolinyl (C ), quinolinyl (C ), 8-hydroxy-quinolinyl
8 8 9
(C ), and isoquinolinyl (C ).
) C -C tethered cyclic hydrocarbyl units (whether carbocyclic units, C or C aryl
1 6 6 10
units, heterocyclic units, or heteroaryl units) which connected to another moiety,
unit, or core of the molecule by way of a C -C alkylene unit. Non-limiting
examples of tethered cyclic hydrocarbyl units include benzyl C -(C ) having the
formula:
wherein R is optionally one or more independently chosen substitutions for
hydrogen. Further examples include other aryl units, inter alia, (2-
hydroxyphenyl)hexyl C -(C ); naphthalenylmethyl C -(C ), 4-fluorobenzyl C -
6 6 1 10 1
(C ), 2-(3-hydroxyphenyl)ethyl C -(C ), as well as substituted and unsubstituted C -
6 2 6 3
C10 alkylenecarbocyclic units, for example, cyclopropylmethyl C1-(C3),
cyclopentylethyl C -(C ), cyclohexylmethyl C -(C );. Included within this category
2 5 1 6
are substituted and unsubstituted C -C alkylene-heteroaryl units, for example a 2-
1 10
picolyl C -(C ) unit having the formula:
wherein R is the same as defined above. In addition, C -C tethered cyclic
1 12
hydrocarbyl units include C -C alkyleneheterocyclic units and alkylene-heteroaryl
1 10
units, non-limiting examples of which include, aziridinylmethyl C -(C ) and oxazol-
2-ylmethyl C -(C ).
For the purposes of the present disclosure carbocyclic rings are from C to C ; aryl
3 20
rings are C or C ; heterocyclic rings are from C to C ; and heteroaryl rings are from C to
6 10 1 9 1
For the purposes of the present disclosure, and to provide consistency in defining the
present disclosure, fused ring units, as well as spirocyclic rings, bicyclic rings and the like,
which comprise a single heteroatom will be characterized and referred to herein as being
encompassed by the cyclic family corresponding to the heteroatom containing ring,
although the artisan may have alternative characterizations. For example, 1,2,3,4-
tetrahydroquinoline having the formula:
is, for the purposes of the present disclosure, considered a heterocyclic unit. 6,7-Dihydro-
5H-cyclopentapyrimidine having the formula:
is, for the purposes of the present disclosure, considered a heteroaryl unit. When a fused
ring unit contains heteroatoms in both a saturated ring (heterocyclic ring) and an aryl ring
(heteroaryl ring), the aryl ring will predominate and determine the type of category to which
the ring is assigned herein for the purposes of describing the invention. For example,
1,2,3,4-tetrahydro-[1,8]naphthpyridine having the formula:
is, for the purposes of the present disclosure, considered a heteroaryl unit.
The term “substituted” is used throughout the specification. The term “substituted”
is applied to the units described herein as “substituted unit or moiety is a hydrocarbyl unit or
moiety, whether acyclic or cyclic, which has one or more hydrogen atoms replaced by a
substituent or several substituents as defined herein below.” The units, when substituting
for hydrogen atoms are capable of replacing one hydrogen atom, two hydrogen atoms, or
three hydrogen atoms of a hydrocarbyl moiety at a time. In addition, these substituents can
replace two hydrogen atoms on two adjacent carbons to form said substituent, new moiety,
or unit. For example, a substituted unit that requires a single hydrogen atom replacement
includes halogen, hydroxyl, and the like. A two hydrogen atom replacement includes
carbonyl, oximino, and the like. A two hydrogen atom replacement from adjacent carbon
atoms includes epoxy, and the like. Three hydrogen replacement includes cyano, and the
like. The term substituted is used throughout the present specification to indicate that a
hydrocarbyl moiety, inter alia, aromatic ring, alkyl chain; can have one or more of the
hydrogen atoms replaced by a substituent. When a moiety is described as “substituted” any
number of the hydrogen atoms may be replaced. For example, 4-hydroxyphenyl is a
“substituted aromatic carbocyclic ring (aryl ring)”, (N,N-dimethylamino)octanyl is a “
substituted C linear alkyl unit, 3-guanidinopropyl is a “substituted C linear alkyl unit,” and
2-carboxypyridinyl is a “substituted heteroaryl unit.”
POLYMER COMPOSITIONS
Disclosed herein are polymer compositions, comprising
a) a base polymer;
b) from about 0.1% to about 10% by weight of an oxygen scavenger; and
c) from about 0.1% to about 10% by weight of a compound further described
herein below.
BASE POLYMERS
The disclosed compositions comprise a base polymer. The base polymer can
comprise one or more homopolymers or copolymers as described herein. The compositions
can comprise from about 80% to about 99.98% by weight of a base polymer. In one
embodiment the composition comprises from about 80% to about 99% by weight of a base
polymer. In another embodiment the composition comprises from about 85% to about 99%
by weight of a base polymer. In a further embodiment the composition comprises from
about 90% to about 99.98% by weight of a base polymer. In a yet further embodiment the
composition comprises from about 95% to about 99% by weight of a base polymer. In a
still further embodiment the composition comprises from about 95% to about 99.98% by
weight of a base polymer. In a yet another embodiment the composition comprises from
about 97% to about 99% by weight of a base polymer.
A variety of different polymers can be used as the base polymer. The disclosed
compositions enable oxygen scavenging, and thus the base polymer generally includes those
polymers that can be subject to oxidation. For example, polymers that exhibit at least some
oxygen permeability are useful with the disclosed compositions, at least inasmuch as the
disclosed compositions can reduce the oxidative damage to the polymer.
The base polymer can be a polymer commonly used in packaging materials including
polyethylene, such as low density polyethylene, very low density polyethylene, ultra-low
density polyethylene, high density polyethylene, and linear low density polyethylene;
polyesters such as (PET), (PEN) and their copolymers such as PET/IP; polyvinyl chloride
(PVC); polyvinylidene chloride (PVDC); and ethylene copolymers such as ethylene/vinyl
acetate copolymer, ethylene/alkyl (meth)acrylate copolymers, ethylene/(meth)acrylic acid
copolymers, and ionomers. Blends of different base polymers also can be used.
In a further aspect, the base polymer can include one or more polymers approved by
the U.S. Food and Drug Administration (FDA). Examples include polyethylene
terephthalate, polypropylene, and polyethylene.
In a further aspect, the base polymer comprises a polyester polymer or copolymer.
Preferred polyesters include polymers of phthalic acids, such as polyethylene terephthalate
(PET), or a copolymer thereof. PET, for example, can be made from terephthalic acid and
ethylene glycol. PET can also be made using dimethyl terephthalate and ethylene glycol.
Preferred copolymers of phthalic acids include copolymers of a phthalic acid and one or
more hydroxylated organic compounds. Examples of suitable hydroxylated organic
compounds include 1, 4-cyclohexandedimethanol, 1,2-propanediol, 1, 4-butanediol, 2,2-
dimethyl-1, 3 -propanediol, 2-methyl -1, 3 -propanediol (2MPDO), 1,6-hexanediol, 1,2-
cyclohexanediol, 1 ,4-cyclohexanediol, 1 ,2-cyclohexanedimethanol, 1,3-
cyclohexanedimethanol, and diols containing one or more oxygen atoms in the chain, e.g.,
diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, or mixtures of
these, and the like.
In a still further aspect, the base polymer includes a polyethylene terephthalate
homopolymer and copolymer modified with one or more polycarboxylic acid modifiers in a
cumulative amount of less than about 15 mole %, or about 10 mole % or less, or about 8
mole % or less, or one or more hydroxyl compound modifiers in an amount of less than
about 60 mol %, or less than about 50 mole %, or less than about 40 mole %, or less than
about 15 mole %, or about 10 mole % or less, or about 8 mole % or less and polyethylene
naphthalate homopolymers and copolymers modified with a cumulative amount of less than
about 15 mole %, or about 10 mole % or less, or about 8 mole % or less, of one or more
polycarboxylic acid modifiers or modified with less than about 60 mol %, or less than about
50 mole %, or less than about 40 mole %, or less than about 15 mole %, or about 10 mole %
or less, or about 8 mole % or less of one or more hydroxyl compound modifiers, and blends
thereof. In some aspects, the base polymer comprises at least 90 mole %, 92 mole %, or 94
mole % ethylene terephthalate repeat units based on the moles of all repeat units in the
polyester polymers.
Polyesters such as PET can be prepared by polymerization procedures known in the
art sufficient to effect esterification and polycondensation. Polyester melt phase
manufacturing processes include direct condensation of a dicarboxylic acid with a diol,
optionally in the presence of one or more esterification catalysts, in the esterification zone,
followed by polycondensation in the prepolymer and finishing zones in the presence of a
polycondensation catalyst; or ester exchange usually in the presence of a transesterification
catalyst in the ester exchange zone, followed by prepolymerization and polymerization in
the presence of a polycondensation catalyst.
OXYGEN SCAVENGER
The compositions comprise from about 0.10% to about 10% weight percent of the
oxygen scavenger. In one embodiment the compositions comprise from about 0.5% to
about 10% by weight of an oxygen scavenger. In another embodiment the compositions
comprise from about 1% to about 5% by weight of an oxygen scavenger. In a further
embodiment the compositions comprise from about 0.1% to about 1% by weight of an
oxygen scavenger. In a still further embodiment the compositions comprise from about
0.1% to about 5% by weight of an oxygen scavenger. In a yet further embodiment the
compositions comprise from about 3% to about 10% by weight of an oxygen scavenger. In
another further embodiment the compositions comprise from about 5% to about 10% by
weight of an oxygen scavenger. In a yet another embodiment the compositions comprise
from about 2% to about 7% by weight of an oxygen scavenger.
Preferably, the oxygen scavenger is an N-allylic oxygen scavenger or N-benzylic
oxygen scavenger. The oxygen scavenger can function as an oxygen scavenger in the
composition. The oxygen scavenging ability of the oxygen scavenger can be enhanced by
the transition metal.
N-allylic or N-benzylic oxygen scavengers have the general structure shown below:
wherein each --- independently denotes an optional covalent bond.
It is also appreciated that an N-allylic or N-benzylic oxygen scavenger can be further
substituted and that more than one amide functionality can be present in a compound. In
one aspect, an N-allylic or N-benzylic oxygen scavenger can be polymeric. In a further
aspect, an N-allylic or N-benzylic oxygen scavenger can be nonpolymeric.
Generally, the oxygen scavenger is present in the composition in an amount of from
0.1 to about 10 weight percent. In one aspect, the oxygen scavenger is present in the
composition in an amount of from 1 to about 10 weight percent. In a further aspect, the
oxygen scavenger is present in the composition in an amount of from 1 to about 5 weight
percent. In a further aspect, the oxygen scavenger is present in the composition in an
amount of from 1 to about 3 weight percent.
In one aspect, the oxygen scavenger has a structure of Formula I:
(I),
wherein each X is selected from the group consisting of O, S, and NH; wherein each Y,
each A, and each B are independently selected from the group consisting of N and CR ;
wherein D, E, and F are independently selected from the group consisting of CH, N, O, and
S; wherein the symbol --- when used in conjunction with a bond line represents a single or a
double bond; and wherein each R is independently selected from the group consisting of H,
alkyl, aryl, electron withdrawing groups, and electron releasing groups.
In a further aspect, the oxygen scavenger has a structure of Formula II:
(II),
wherein each X is selected from the group consisting of O, S, and NH; wherein each Y,
each A, and each B are independently selected from the group consisting of N and CR ;
wherein D, E, and F are independently selected from the group consisting of CH, N, O, and
S; wherein the symbol --- when used in conjunction with a bond line represents a single or a
double bond; and wherein each R is independently selected from the group consisting of H,
alkyl, aryl, electron withdrawing groups, and electron releasing groups.
The alkyl group of Formula (I) or (II) can be a branched or unbranched saturated
hydrocarbon group of 1 to 24 carbon atoms, e.g. 1 to 18 carbons atoms, 1 to 14 carbon
atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8, 1 to 6 carbon atoms, or 1 to 4
carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl,
hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl
group can be substituted or unsubstituted. The alkyl group can be substituted with one or
more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl,
aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, halide, hydroxamate, hydroxy,
ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below. The
alkyl group can be halogenated, which includes an alkyl group that is substituted with one
or more halide, e.g., fluorine, chlorine, bromine, or iodine. The alkyl group can also be a
lower alkyl group, which is an alkyl group containing from one to six (e.g., from one to
four) carbon atoms.
The aryl group of Formula (I) or (II) can be any carbon-based aromatic group
including but not limited to, benzene, naphthalene, phenyl, biphenyl, etc. The aryl group
can also be heteroaryl, which is defined as an aromatic group that has at least one
heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms
include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group can
be substituted or unsubstituted. The aryl group can be substituted with one or more groups
including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl,
heteroaryl, aldehyde, amino, carboxylic acid, ester, halide, hydroxamate, hydroxy, ketone,
nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein. A biaryl
group is a specific type of aryl group and is included in the definition of aryl. Biaryl refers
to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or
are attached via one or more carbon-carbon bonds, as in biphenyl.
Suitable electron withdrawing groups and electron releasing groups are generally
known in the art. Preferred electron withdrawing groups include nitro, carboxylic acid,
esters, for example loweralkyl esters, and cyano. Preferred electron releasing groups include
branched and straight chain alkyl groups, for example, methyl, ethyl, propyl, isopropyl,
butyl, isobutyl, and tert-butyl. Other preferred electron releasing groups include alkoxy, for
example methoxy and ethoxy. Other preferred electron releasing groups include thioalkyl.
Still other preferred electron releasing groups include amines, for example –NH , and
NH(loweralkyl) and N(loweralkyl) .
Preferred oxygen scavengers of Formula (I) and (II) are disclosed in U.S. Patent
Application Publication No. 20080277622, Deshpande et al. “Oxygen Scavenging
Molecules, Articles Containing Same, And Methods of Their Use,” which is incorporated
herein by this reference for its teaching of oxygen scavengers, their preparation, and their
use as oxygen scavenging materials.
In a further aspect, the oxygen scavenger is polymeric or copolymeric and comprises
a structure of Formula III:
(III),
wherein m is a positive integer greater than 10; wherein n is an integer from 1 to 6; and
wherein R is H or C1-C4 alkyl. The C1-C4 alkyl group can be substituted or unsubstituted
methyl, ethyl, propyl, butyl, isopropyl, or isobutyl. In a further aspect, R is H. In one
aspect, n is 4. One example of a compound of Formula III is MXD6 (available
commercially, e.g., from Mitsubishi Gas Chemicals of Japan). MXD6 is a polymer
produced by condensation of meta-xylylene diamine and adipic acid. Compounds of
Formula III can be obtained from commercial sources or be prepared by polymerization
methods known in the art. Suitable grades include HB-5299 from EMS Grivory; 6001,
6003, 6007 and 6121 from Mitsubishi Gas and Chemical Company.
In one aspect, the oxygen scavenger has a structure of Formula I: the oxygen
scavenger has a structure represented by a formula:
E-(L-E)
wherein x is 0, 1, or 2; wherein E has a structure of Formula IV or Formula V:
(IV)
(V),
21 21
wherein L is a linking group of the formula -(O-R ) -O-, -(NH-R ) -NH-, -(NH-
22 25 26 25 23 24
C(=O)R ) -NH, -NH-R -NH(C(=O)R NHR NH) -, -(O-R -O-R -C(=O) -O)- where L
t u s
12 13
is attached to a carbon atom of at least one Ar in Formula IV or where R and/or R of
1 2 11
Formula V is L; wherein Ar is aryl or heteroaryl; wherein R , R , and R are each
independently, H, C -C alkyl, C -C alkoxy, C -C aryloxy, hydroxy, C -C alkenyl,
1 12 1 6 6 20 2 6
19 20 1 2
NR R , acetyl, nitro, glyceryl, carbohydrate, -C(=O)H, L, or two R or two R groups can
18 3 4 14 15 5 10
form a group of the formula -O-R -O; wherein R , R , R , and R are each H; R to R
16 17 12 13
and R , and R are each, independently, H or C -C alkyl; R and R are each,
independently, H, C -C alkyl, C -C aryl, C -C alkoxy, or L; wherein R is C -C alkyl;
1 6 6 20 1 6 2 6
19 20 2 24
R and R are each, independently, H, C1-C6 alkyl, or C6-C20 aryl; wherein R , and R are
22 23 25 26
each, independently, C -C alkyl; wherein R , R , R and R are each, independently, C -
1 6 1
C alkyl or C -C aryl; wherein n and p are independently 0 or an integer from 1 to 5;
6 6 20
wherein q is 0 or an integer from 1 to 4; wherein s and z are independently 1, 2, or 3; and
wherein t and u are independently 1 or 2.
In a further aspect, E has a structure of Formula IV:
(IV).
In a further aspect, the oxygen scavenger has a structure represented by a formula:
In a further aspect, n and p are each 0, 1, or 2 and R1 and R are each independently
H, C -C alkyl, hydroxy, C -C alkoxy, or carbohydrate. In a further aspect, R and R are
1 4 1 3
each independently H, methyl, ethyl, hydroxy, methoxy, ethoxy, or glucose. In a further
10 1 2
aspect, R to R are each H. In a further aspect, R and R are each H. In a further aspect,
the oxygen scavenger has a structure represented by a formula:
In a further aspect, E has a structure of Formula V:
(V).
In a further aspect, the oxygen scavenger has a structure represented by a formula:
16 17 11
In a further aspect, R and R are H. In a further aspect, each R is independently
H, C -C alkyl, hydroxy, or C -C alkoxy, or carbohydrate. In a further aspect, each R is
1 4 1 3
independently H, methyl, ethyl, hydroxy, methoxy, or ethoxy. In a further aspect, the
oxygen scavenger has a structure represented by a formula:
Preferred oxygen scavengers of Formula (IV) and (V) are disclosed in U.S. Patent
Application Publication No. 20060180790, Deshpande et al. “Oxygen scavenging
compositions and packaging comprising said compositions,” which is incorporated herein
by this reference for its teaching of oxygen scavengers, their preparation, and their use as
oxygen scavenging materials.
In other aspects, the oxygen scavenger can be any one or more of the conventionally
known polybutadiene based oxygen scavengers. Exemplary and non-limiting examples of
commercially available polybutadiene based oxygen scavengers include the Amosorb® line
of oxygen scavengers available from ColorMatrix of Berea, Ohio, USA.
COMPOUNDS
Disclosed herein are compounds capable of being formulated with one or more base
polymers wherein the compounds when formulated with the one or more base polymers to
provide a polymer composition that can serve as a barrier to slow, retard, or stop the flow of
carbon dioxide or water vapor or other gaseous/organoleptic transport through the polymer
composition.
The compositions comprise from about 0.10% to about 10% weight percent of the
compound. In one embodiment the compositions comprise from about 0.5% to about 10%
by weight of an compound. In another embodiment the compositions comprise from about
1% to about 5% by weight of an compound. In a further embodiment the compositions
comprise from about 0.1% to about 1% by weight of an compound. In a still further
embodiment the compositions comprise from about 0.1% to about 5% by weight of an
compound. In a yet further embodiment the compositions comprise from about 3% to about
% by weight of an compound. In another further embodiment the compositions comprise
from about 5% to about 10% by weight of an compound. In a yet another embodiment the
compositions comprise from about 2% to about 7% by weight of an compound.
The compounds that can be formulated with the base polymer have the formula:
wherein R to R are each independently chosen from:
i) hydrogen;
ii) C -C substituted or unsubstituted linear, branched, or cyclic alkyl;
1 12
iii) C -C substituted or unsubstituted linear, branched, or cyclic alkenyl;
2 12
iv) C -C substituted or unsubstituted linear or branched alkynyl;
2 12
v) C or C substituted or unsubstituted aryl;
6 10
vi) C -C substituted or unsubstituted heterocyclic;
vii) C -C substituted or unsubstituted heteroaryl;
1 11
10a 10b 11
viii) –[C(R )(R )] OR ;
wherein R is chosen from:
a) –H;
b) C -C substituted or unsubstituted linear, branched, or cyclic alkyl or
1 12
C -C substituted or unsubstituted linear, branched, or cyclic
1 12
haloalkyl;
c) C or C substituted or unsubstituted aryl or C -C alkylenearyl;
6 10 7 20
d) C -C substituted or unsubstituted heterocyclic; and
e) C -C substituted or unsubstituted heteroaryl;
1 11
10a 10b 12a 12b
ix) –[C(R )(R )] N(R )(R );
12a 12b
wherein R and R are each independently chosen from:
a) –H;
b) –OR ;
R is hydrogen or C -C4 linear alkyl;
c) C -C substituted or unsubstituted linear, branched, or cyclic alkyl;
1 12
d) C or C substituted or unsubstituted aryl;
6 10
e) C -C substituted or unsubstituted heterocyclic;
f) C -C substituted or unsubstituted heteroaryl; and
1 11
12a 12b
g) R and R can be taken together to form a substituted or
unsubstituted ring having from 3 to 10 carbon atoms and from 0 to 3
heteroatoms chosen from oxygen, nitrogen, and sulfur;
10a 10b 14
x) –[C(R )(R )] C(O)R ;
wherein R is chosen from:
a) C -C substituted or unsubstituted linear, branched, or cyclic alkyl;
1 12
b) –OR ;
wherein R is hydrogen, substituted or unsubstituted C -C linear
alkyl, C or C substituted or unsubstituted aryl, C -C substituted or
6 10 1 9
unsubstituted heterocyclic, C -C substituted or unsubstituted
1 11
heteroaryl; and
16a 16b
c) –N(R )(R );
16a 16b
wherein R and R are each independently hydrogen, C -C
1 12
substituted or unsubstituted linear, branched, or cyclic alkyl; C or C-
substituted or unsubstituted aryl; C -C substituted or unsubstituted
1 9
heterocyclic; C -C substituted or unsubstituted heteroaryl; or R
1 11
and R can be taken together to form a substituted or unsubstituted
ring having from 3 to 10 carbon atoms and from 0 to 3 heteroatoms
chosen from oxygen, nitrogen, and sulfur;
10a 10b 17
xi) –[C(R )(R )] OC(O)R ;
wherein R is chosen from:
a) C1-C12 substituted or unsubstituted linear, branched, or cyclic alkyl;
18a 18b
b) –N(R )(R );
18a 18b
R and R are each independently hydrogen, C -C substituted or
1 12
unsubstituted linear, branched, or cyclic alkyl; C or C substituted
6 10
or unsubstituted aryl; C -C substituted or unsubstituted heterocyclic;
18a 18b
C -C substituted or unsubstituted heteroaryl; or R and R can be
1 11
taken together to form a substituted or unsubstituted ring having from
3 to 10 carbon atoms and from 0 to 3 heteroatoms chosen from
oxygen, nitrogen, and sulfur;
10a 10b 19 20
xii) –[C(R )(R )] NR C(O)R ;
wherein R is chosen from:
a) –H; and
b) C -C substituted or unsubstituted linear, branched, or cyclic alkyl;
wherein R is chosen from:
a) C -C substituted or unsubstituted linear, branched, or cyclic alkyl;
1 12
21a 21b
b) –N(R )(R );
21a 21b
R and R are each independently hydrogen, C -C substituted or
1 12
unsubstituted linear, branched, or cyclic alkyl; C or C substituted
6 10
or unsubstituted aryl; C -C substituted or unsubstituted heterocyclic;
21a 21b
C -C substituted or unsubstituted heteroaryl; or R and R can be
1 11
taken together to form a substituted or unsubstituted ring having from
3 to 10 carbon atoms and from 0 to 3 heteroatoms chosen from
oxygen, nitrogen, and sulfur;
10a 10b
xiii) –[C(R )(R )] CN;
10a 10b
xiv) –[C(R )(R )] NO ;
10a 10b 22
xv) –[C(R )(R )] SO R ;
R is hydrogen, hydroxyl, substituted or unsubstituted C -C linear or
branched alkyl; substituted or unsubstituted C , C , or C aryl; C -C
6 10 14 7 15
alkylenearyl; C -C substituted or unsubstituted heterocyclic; or C -C
1 9 1 11
substituted or unsubstituted heteroaryl; and
xvi) halogen;
10a 10b
xvii) –[C(R )(R )] (CH X ) CH X ; wherein X is halogen, the index j is an
y j’ k’ h j k
integer from 0 to 2, the index k is an integer from 1 to 3, j + k = 3; the index
j’ is an integer from 0 to 2, the index k’ is and integer from 0 to 2, j’ + k’ = 2;
the index h is from 0 to 5;
10a 10b
R and R are each independently hydrogen or C -C alkyl; and
the index y is from 0 to 5;
R and R can be taken together to from a 5 to 7 member ring containing
from 3 to 7 carbon atoms and from 0 to 2 heteroatoms chosen from oxygen,
sulfur, or nitrogen, wherein one or more of the carbon atoms can be
substituted, unsubstituted, or a carbonyl unit.
As described herein above, the various units that comprise R to R can be
substituted by one or more units independently chosen from:
i) C -C linear, branched, or cyclic alkyl, alkenyl, and alkynyl;
1 12
ii) C -C linear, branched, or cyclic alkoxy, alkenyloxy, and alkynyloxy;
1 12
iii) C -C linear, branched, or cyclic haloalkyl, haloalkenyl, and haloalkynyl;
1 12
iv) C or C aryl;
6 10
v) C or C alkylenearyl;
6 10
vi) C -C heterocyclic rings;
vii) C -C heteroaryl rings;
102a 102b 101
viii) –(CR R ) OR ;
102a 102b 101
ix) –(CR R ) C(O)R ;
102a 102b 101
x) –(CR R ) C(O)OR ;
102a 102b 101
xi) –(CR R ) C(O)N(R ) ;
102a 102b 101
xii) –(CR R ) N(R ) ;
xiii) halogen;
102a 102b
xiv) –(CR R ) CN;
102a 102b
xv) –(CR R ) NO ;
xvi) –CH X ; wherein X is halogen, the index j is an integer from 0 to 2, j + k =
3; for example,
102a 102b 101
xvii) –(CR R ) SR ;
102a 102b 101
xviii) –(CR R ) SO R and
102a 102b 101
xix) –(CR R ) SO R ;
wherein each R is independently hydrogen, substituted or unsubstituted C -C
linear, branched, or cyclic alkyl, phenyl, benzyl, heterocyclic, or heteroaryl; or two
101 102a 102b
R units can be taken together to form a ring comprising 3-7 atoms; R and R
are each independently hydrogen or C1-C4 linear or branched alkyl; the index z is
from 0 to 4.
One aspect of the present disclosure relates to compounds wherein R and R can be
taken together to from a 5 to 7 member ring containing from 3 to 7 carbon atoms and from 0
to 2 heteroatoms chosen from oxygen, sulfur, or nitrogen, wherein one or more of the
carbon atoms can be substituted, unsubstituted, or a carbonyl unit.
One embodiment of this aspect relates to compounds wherein R and R are taken
together to form a 6-member ring, for example, compounds chosen from:
i) benzo[de]isochromen-1(3H)-one having the formula:
ii) 1H-benzo[de]isoquinoline-1,3(2H)-dione having the formula:
iii) 2,3-dihydro-1H-benzo[de]isoquinolinone having the formula:
; and
iv) benzo[de]-isochromene-1,3-dione having the formula:
Another aspect of the present disclosure as it relates to compounds includes
compounds having the formula:
wherein R and R are each independently:
i) hydrogen; or
ii) –C(O)R ;
14 15 16a 16b 15 16a 16b
wherein R is –OR or –N(R )(R ); R is hydrogen or methyl; R and R are each
independently hydrogen or methyl. A non-limiting example of this aspect is naphthalene-
1,8-dicarboxyamide having the formula:
For example, if a compound benzo[de]-isochromene-1,3-dione (1,8-Naphthalic
Anhydride) is added to PET, the molecular size of benzo[de]-isochromene-1,3-dione (1,8-
Naphthalic Anhydride) is just smaller than the free volume of PET at room temperature. A
typical PET resin used in bottles has a molecular weight of ~ 28,000. Free volume of PET at
room temperature is around 1301 (Angstrom) (Reference: Polyakova, A, et.al., Journal of
Polymer Science: Part B: Polymer Physics, Vol 39, pages 1889-1899, year 2001).
Molecular volume of benzo[de]-isochromene-1,3-dione (1,8-Naphthalic Anhydride) and
1H-benzo[de]isoquinoline-1,3(2H)-dione (1,8-Napthalimide) is 872 (Angstrom) and 889
(Angstrom) (Reference: Lieh Nguyen Shok and G. A. Gol’der, Translated from Zhurnal
Strukturnoi Khimii, Vol. 11, No. 5, pp. 939-940, September-October 1970). As seen from
the molecular volume numbers, it is clear that benzo[de]-isochromene-1,3-dione (1,8-
Naphthalic Anhydride) and 1H-benzo[de]isoquinoline-1,3(2H)-dione (1,8-Napthalimide)
molecules can fit inside the free volume of individual PET chains – and reduce the free
volume of PET by as much as 68%. This reduction in free volume due to incorporation of
additives described above increase the hop distance for CO diffusion through PET, thereby
reducing the CO permeation rate and increasing shelf life of carbonated soft drink (CSD)
and beer bottles.
Various methods exist for making the composition. In one aspect, the composition
can be made by mixing the base polymer with the oxygen scavenger and the compound. In
another aspect, the composition can be made by mixing the base polymer with the
compound. In some aspects, the base polymer, the oxygen scavenger and the compound are
mixed by tumbling in a hopper. Other optional ingredients can be added during this mixing
process or added to the mixture after the aforementioned mixing or to an individual
component prior to the aforementioned mixing step.
When melt processing is desired for the composition, the composition can also be
made by adding each ingredient separately and mixing the ingredients just prior melt
processing the composition to form an article. In some embodiments, the mixing can be
just prior to the melt process zone. In other embodiments, one or more ingredients can be
premixed in a separate step prior to bringing all of the ingredients together.
In some aspects, the compound can be added neat or in a carrier (such as a liquid or
wax) to an extruder or other device for making the article, or the compound can be present
in a concentrate or carrier with the oxygen scavenger, in a concentrate or carrier with the
base polymer, or in a concentrate or carrier with a base polymer/oxygen scavenger blend. It
is desirable that the addition of the compound does not substantially increase the intrinsic
viscosity of the melt in the melt processing zone. Thus, compounds can be added in two or
more stages, such as once during the melt phase for the production of the base polymer and
again once more to the melting zone for making the article.
The melt blend of base polymer, oxygen scavenger, and compound can also be
prepared by adding the components at the throat of an injection molding machine that: (i)
produces a preform that can be stretch blow molded into the shape of the container, (ii)
produces a film that can be oriented into a packaging film, (iii) produces a sheet that can be
thermoformed into a food tray, or (iv) produces an injection molded container. The mixing
section of the extruder should be of a design to produce a homogeneous blend. Such process
steps work well for forming carbonated soft drink, water or beer bottles, packaging films
and thermoformed trays. The present invention can be employed in any of the conventional
known processes for producing a polymeric container, film, tray, or other article that would
benefit from oxygen scavenging.
ARTICLES
Various articles can be prepared from the disclosed compositions. Thus, the articles
prepared from the compositions will also have the composition present in the article.
Suitable articles include vessels and films, such as flexible sheet films, flexible bags,
pouches, semi-rigid and rigid containers such as bottles (e.g. PET bottles) or combinations
thereof. Typical flexible films and bags include those used to package various food items
and can be made up of one or a multiplicity of layers to form the overall film or bag-like
packaging material. The disclosed compositions can be used in one, some or all of the
layers of such packaging material.
Specific articles include preforms, containers and films for packaging of food,
beverages, cosmetics, pharmaceuticals, and personal care products where a high carbon
dioxide or moisture or organoleptic barrier is needed. Examples of beverage containers are
bottles for holding water and carbonated soft drinks, and the invention is particularly useful
in bottle applications containing juices, sport drinks, beer or any other beverage where loss
of carbon dioxide detrimentally affects the flavor, fragrance, performance (e.g., vitamin
degradation),. The compositions can also be useful as a sheet for thermoforming into rigid
packages and films for flexible structures – to deliver organoleptic and moisture barrier.
Rigid packages include food trays and lids. The compositions can also be used in the
manufacture of cosmetic containers and containers for pharmaceuticals or medical devices.
Other suitable articles include rigid or semi-rigid articles including plastic, such as
those utilized for juices, soft drinks, as well as thermoformed trays or cup normally having
thickness in the range of from 100 to 1000 micrometers. The walls of such articles can
comprise single or multiple layers of materials. The article can also take the form of a
bottle or can, or a crown, cap, crown or cap liner, plastisol or gasket (if the part is made up
of PET). As a liner, the composition can be extruded as a film along with the rigid article
itself, e.g., by coextrusion, extrusion coating, or an extrusion lamination process, so as to
form the liner in situ during article production; or alternatively can be adhered by heat
and/or pressure, by adhesive, or by any other suitable method (as long as the liner is
comprised of PET).
Besides articles applicable for packaging food and beverage, articles for packaging
other carbon dioxide-sensitive products can also benefit from the present invention. Such
products would include modified atmosphere packaging of fruits and vegetables, medical
devices and the like.
In a further aspect, the composition can be used as a master batch for blending with
a polymer or a polymer containing component. In such compositions, the concentration of
the compound will be high enough to allow for the final blended product to have suitable
amounts of these components. The master batch can also contain an amount of the base
polymer with which the master batch is blended.
The articles can be made by various methods known in the art. Generally, the
articles are prepared by melt processing methods (i.e., a melt of the composition). Such
processes generally include injection molding, stretch blow molding, extrusion,
thermoforming, extrusion blow molding, and (specifically for multilayer structures) co-
extrusion and lamination using adhesive tie layers. Orientation, e.g., by stretch blow
molding, of the polymer can be used with phthalate polyesters because of the known
mechanical advantages that result.
The melt processing zone for making the article can be operated under customary
conditions effective for making the intended articles, such as preforms, bottles, trays, and
other articles mentioned above. In one aspect, such conditions are effective to process the
melt without substantially increasing the intrinsic viscosity of the melt and which are
ineffective at promoting transesterification reactions. In some preferred aspects, suitable
operating conditions effective to establish a physical blend of the base polymer, oxidizable
organic component, and transition metal are temperatures in the melt processing zone
within a range of about 250 °C to about 300 °C at a total cycle time of less than about 6
minutes, and typically without the application of vacuum and under a positive pressure
ranging from about 0 psig (pound-force per square inch gauge) to about 900 psig. In some
embodiments, the residence time of the melt on the screw can range from about 1 to about 6
minutes.
EXAMPLE 1
A 21.6 gram polyethylene terephthalate preform comprising compounds as disclosed
herein was prepared on a 2-cavity Husky LX 160 injection molding machine under standard
injection conditions. The following table (Table 1) compares the examples according to the
present disclosure with samples comprising the disclosed compounds and a sample wherein
caffeine substitutes for the disclosed compounds.
Table 1.
Run Caff benzo[de]-isochromene- benzo[de]isoquinoline-1,3-
No. eine 1,3-dione dione
6821-1 Parastar 7000 -- -- --
6696-2 Parastar 7000 5% -- --
6696-4 Parastar 7000 -- 2.5% --
6696-3 Parastar 7000 -- -- 2.5%
6821-2 Parastar 7000 10% -- --
6821-4 Parastar 7000 -- 5% --
6821-3 Parastar 7000 -- -- 5%
Parastar 7000 is a commercially available PET resin available from Eastman Chemical Co.,
Kingsport, Tennessee, USA.
The preforms were blown into a 12 oz. carbonated soft drink (CSD) container on
Sidel’s SBO 2/3 blow molding machine. The 12 oz. CSD bottles were then tested for CO
retention using Quantiperm Model 504 (manufactured by Quantiperm, LLC). This
instrument allows direct, real-time measurement of CO loss from plastic bottles. Prior to
testing the bottles are filled with carbonated water till 4.2 gas volumes of CO for
approximately one week in the preconditioning phase. After preconditioning phase is
complete, the CO efflux through the bottle wall is at a substantially constant rate. The
Quantiperm instrument measures this steady state loss rate rapidly and directly. The real
time loss rates are combined with the driving force (CO partial pressure within the
packages) to make accurate shelf life estimation for carbonated packages. A barrier
improvement factor (BIF) can be determined by taking a ratio of the time taken for 20%
CO loss for the control package and the test package.
Figures 1, 2(a), and 2(b) show CO loss as a function of time for variables 6821-1,
6821-2, 6821-3 and 6821-4, as measured by Quantiperm Model 504. Addition of 5%
benzo[de]isochromene-1,3-dione and 5% benzo[de]isoquinoline-1,3-dione to PET reduces
the rate of CO loss, with a BIF of ~ 1.67X over PET. Variable 6821-2 did not offer as
much improvement (BIF = 1.1X) as Variables 6821-3 and 6821-4. As seen from Figures 3,
6696-2 did not offer a substantial BIF over PET, but 6696-3 and 6696-4 showed improved
performance, with a BIF of ~ 1.2X.
EXAMPLE 2
A 35.5 gram PET preform for a 16 oz. stock beer bottle comprising compounds as
disclosed herein was prepared on a 2-cavity Husky LX 160 injection molding machine
under standard injection conditions. The following table (Table 2) compares the examples
according to the present disclosure with samples comprising the disclosed compounds.
Table 2.
Run # PET used Additive used Wt % of additive
8139-1 (Control) Parastar 7000 None
8139-2 Parastar 7000 ColorMatrix Process Aid 801 1%
8139-3 Parastar 7000 ColorMatrix Process Aid 801 0.6%
8139-4 Parastar 7000 Croda’s Atmer 7150 5%
8139-5 Parastar 7000 Techmer 13350 5%
8139-6 Parastar 7000 1,8-Naphthalic Anhydride 5%
(benzo[de]-isochromene-1,3-
dione)
8139-7 Parastar 7000 1,8-Naphthalic Anhydride 4%
ColorMatrix Process Aid 801 0.4%
The preforms were blown into 16 oz. beer bottles on Sidel’s SBO 2/3 blow molding
machine. The preform heating zone profile for SBO 2/3 are shown in Table 3 below.
Table 3.
Zone % Power Bulb distance from Oven 1 Oven 2 Oven 3
from preform support ON/OFF ON/OFF ON/OFF
2000 W ledge (mm)
lamp
1 98% 7.5 ON ON ON
2 88% 22.5 ON ON ON
3 46% 37.5 OFF ON OFF
4 40% 52.5 ON ON OFF
45% 67.5 OFF ON ON
6 45% 82.5 OFF OFF ON
7 51% 97.5 ON ON ON
The preforms were blown on a cold mold (at 55 F) by using a 12 mm diameter
stretch rod, 40 bar air pressure and at a machine speed of ~ 1500 bottles/hour . The preform
heat setting (shown in Table 3) resulted in INT of 103 F as measured by infrared
thermometer aimed at zone 3 of the preform coming out of the heating zone.
The 16 oz. beer bottles were then tested for CO retention, O Transmission Rate
(OTR) and WVTR (water vapor transmission rate) to determine the effect of various
additives on gas permeation.
A brief description of the apparatus (Quantiperm Model 504) used to measure CO
transmission rate is shown in Example 1. Figures 4 and 5 show CO loss as a function of
time for variables 8139-1, 8139-2, 8139-3, 8139-4, 8139-5, 8139-6 and 8139-7, as measured
by Quantiperm Model 504. For beer bottles, shelf life is determined by measuring the time
required for 15% CO loss from initial carbonation levels. The shelf life and CO BIF for
different variables is shown in Table 4 below:
Table 4.
Example 2, Shelf life (weeks) CO BIF OTR cc/pkg/day O BIF
Run # Measured by (measured by
Quantiperm Iliop)
8139-1 9 1X 0.0309 1X
(CONTROL)
8139-2 9 1X 0.0285 1.08X
8139-3 11 1.22X 0.0284 1.09X
8139-4 9 1X 0.0307 1X
8139-5 10 1.11 0.0296 1.04X
8139-6 13 1.44X 0.0199 1.55X
8139-7 14 1.56X 0.0208 1.49X
Addition of 4% benzo[de]isochromene-1,3-dione and 0.4% Fatty Acid Ester such as
ColorMatrix Process Aid 801 to PET (Run 8139-7) reduces the rate of CO loss, with
a BIF of ~ 1.56X over PET. Variable 8139-2 and 8139-4 did not offer any improvement in
CO barrier – indicating the use of fatty acid esters by themselves have negligible effect on
reducing the CO permeation through PET bottle. Addition of 5% benzo[de]-isochromene-
1,3-dione (1,8-Naphthalic Anhydride) to PET (Run 8139-6) did increase the shelf life by
1.44X over Control PET beer bottle. This result is similar to the result described in Example
In addition to CO2 permeation rate measurements, the bottles of Example 2 were
tested for O transmission rates (OTR) using Illiop. The OTR data show that addition of
benzo[de]-isochromene-1,3-dione (1,8-Naphthalic Anhydride) to PET (in Run 8139-6 and
8139-7) resulted in reduction in OTR along with a reduction of CO2 TR (as seen from an
increase in shelf life).
While particular embodiments of the present disclosure have been illustrated and
described, it would be obvious to those skilled in the art that various other changes and
modifications can be made without departing from the spirit and scope of the disclosure. It
is therefore intended to cover in the appended claims all such changes and modifications
that are within the scope of this disclosure.
Claims (27)
1. A polymer composition, comprising: a) a base polymer; and b) from about 0.1% to about 10% by weight of a compound having the formula: wherein R and R are each independently chosen from: i) C -C linear, branched, or cyclic alkyl; 1 12 ii) C -C linear, branched, or cyclic alkenyl; 2 12 iii) C -C linear or branched alkynyl; 2 12 iv) C or C aryl; 6 10 10a 10b 11 v) –[C(R )(R )] OR ; wherein R is chosen from: a) –H; b) C -C linear, branched, or cyclic alkyl or C -C linear, 1 12 1 12 branched, or cyclic haloalkyl; and c) C or C aryl or C -C alkylenearyl; 6 10 7 20 10a 10b 12a 12b vi) –[C(R )(R )] N(R )(R ); 12a 12b wherein R and R are each independently chosen from: a) –H; b) –OR ; R is hydrogen or C -C linear alkyl; c) C -C linear, branched, or cyclic alkyl; and 1 12 d) C or C aryl; 6 10 10a 10b 14 vii) –[C(R )(R )] C(O)R ; wherein R is chosen from: a) C -C linear, branched, or cyclic alkyl; 1 12 b) –OR ; wherein R is hydrogen, C -C linear alkyl, or C or C aryl; 1 4 6 10 16a 16b c) –N(R )(R ); 16a 16b wherein R and R are each independently hydrogen, C - C linear, branched, or cyclic alkyl; or C or C aryl; 12 6 10 10a 10b 17 viii) –[C(R )(R )] OC(O)R ; wherein R is chosen from: a) C -C linear, branched, or cyclic alkyl; and 1 12 18a 18b b) –N(R )(R ); 18a 18b R and R are each independently hydrogen, C -C linear, 1 12 branched, or cyclic alkyl; or C or C aryl; 6 10 10a 10b 19 20 ix) –[C(R )(R )] NR C(O)R ; wherein R is chosen from: a) –H; and b) C -C linear, branched, or cyclic alkyl; wherein R is chosen from: a) C -C linear, branched, or cyclic alkyl; and 1 12 21a 21b b) –N(R )(R ); 21a 21b R and R are each independently hydrogen, C -C linear, 1 12 branched, or cyclic alkyl; or C or C aryl; 6 10 10a 10b x) –[C(R )(R )] CN; 10a 10b xi) –[C(R )(R )] NO ; 10a 10b 22 xii) –[C(R )(R )] SO R ; R is hydrogen, hydroxyl, C -C linear or branched alkyl; C , C , or 1 4 6 10 C aryl; C -C alkylenearyl; C -C heterocyclic; or C -C 14 7 15 1 9 1 11 heteroaryl; and xiii) halogen; 10a 10b xiv) –[C(R )(R )] (CH X ) CH X ; wherein X is halogen, the index j y j’ k’ h j k is an integer from 0 to 2, the index k is an integer from 1 to 3, j + k = 3; the index j’ is an integer from 0 to 2, the index k’ is and integer from 0 to 2, j’ + k’ = 2; the index h is from 0 to 5; 10a 10b R and R are each independently hydrogen or C -C alkyl; and the index y is from 0 to 5; R and R can be taken together to form a 6 member ring containing from 4 to 6 carbon atoms and from 0 to 2 heteroatoms chosen from oxygen, sulfur, or nitrogen, wherein one or more of the carbon atoms can be a carbonyl unit; wherein R to R are each hydrogen.
2. The composition according to Claim 1, wherein R and R are each independently chosen from: i) C -C linear, branched, or cyclic alkyl, alkenyl, and alkynyl; 1 12 ii) C -C linear, branched, or cyclic alkoxy, alkenyloxy, and alkynyloxy; 1 12 iii) C -C linear, branched, or cyclic haloalkyl, haloalkenyl, and haloalkynyl; 1 12 iv) C or C aryl; 6 10 v) C or C alkylenearyl; 6 10 102a 102b 101 vi) –(CR R ) OR ; 102a 102b 101 vii) –(CR R ) C(O)R ; 102a 102b 101 viii) –(CR R )zC(O)OR ; 102a 102b 101 ix) –(CR R ) C(O)N(R ) ; 102a 102b 101 x) –(CR R ) N(R ) ; xi) halogen; 102a 102b xii) –(CR R ) CN; 102a 102b xiii) –(CR R ) NO ; xiv) –CH X ; wherein X is halogen, the index j is an integer from 0 to 2, j + k = 102a 102b 101 xv) –(CR R ) SR ; 102a 102b 101 xvi) –(CR R ) SO R and 102a 102b 101 xvii) –(CR R )zSO3R ; wherein each R is independently hydrogen, C -C linear, branched, or cyclic 102a 102b alkyl, phenyl, or benzyl; R and R are each independently hydrogen or C -C linear or branched alkyl; the index z is from 0 to 4.
3. The composition according to Claim 1, wherein R and R can be taken together to form a 6 member ring containing from 4 to 5 carbon atoms and 1 or 2 heteroatoms chosen from oxygen, sulfur, or nitrogen, wherein one or more of the carbon atoms is a carbonyl unit.
4. The composition according to Claim 1, wherein the compound is chosen from: i) benzo[de]isochromen-1(3H)-one having the formula: ii) 1H-benzo[de]isoquinoline-1,3(2H)-dione having the formula: ; and iii) 2,3-dihydro-1H-benzo[de]isoquinolinone having the formula:
5. The composition according to Claim 1, wherein the compound is benzo[de]- isochromene-1,3-dione having the formula:
6. The composition according to Claim 1, wherein the compound has the formula: 1 8 14 R and R are each independently –C(O)R ; 14 15 16a 16b 15 16a 16b wherein R is –OR or –N(R )(R ); R is hydrogen or methyl; R and R are each independently hydrogen or methyl.
7. The composition according to Claim 1, wherein the compound is naphthalene-1,8- dicarboxamide having the formula:
8. The composition according to Claim 1, wherein the composition further comprises an oxygen scavenger and wherein the oxygen scavenger is an N-allylic amide or N- benzylic amide.
9. The composition according to Claim 1, wherein the base polymer comprises a polyester.
10. The composition according to Claim 1, wherein the base polymer comprises polyethylene terephthalate or a copolymer thereof.
11. The polymer composition of Claim 1, wherein the base polymer comprises polypropylene.
12. A preform comprising the composition according to any one of Claims 1 to 11.
13. An article of manufacture comprising the composition according to any one of Claims 1 to 11.
14. The article according to Claim 13, wherein the article is a monolayered article.
15. An article of manufacture, comprising: a) a base polymer; b) from about 0.1% to about 10% by weight of a compound having the formula: wherein R and R are each independently chosen from: i) C -C linear, branched, or cyclic alkyl; 1 12 ii) C -C linear, branched, or cyclic alkenyl; 2 12 iii) C -C linear or branched alkynyl; 2 12 iv) C or C aryl; 6 10 10a 10b 11 v) –[C(R )(R )] OR ; wherein R is chosen from: a) –H; b) C -C linear, branched, or cyclic alkyl or C -C linear, 1 12 1 12 branched, or cyclic haloalkyl; c) C or C aryl or C -C alkylenearyl; 6 10 7 20 10a 10b 12a 12b vi) –[C(R )(R )] N(R )(R ); 12a 12b wherein R and R are each independently chosen from: a) –H; b) –OR ; R is hydrogen or C -C4 linear alkyl; c) C1-C12 linear, branched, or cyclic alkyl; d) C or C aryl; 6 10 10a 10b 14 vii) –[C(R )(R )] C(O)R ; wherein R is chosen from: a) C -C linear, branched, or cyclic alkyl; 1 12 b) –OR ; wherein R is hydrogen, C -C linear alkyl, or C or C aryl; 1 4 6 10 16a 16b c) –N(R )(R ); 16a 16b wherein R and R are each independently hydrogen, C - C12 linear, branched, or cyclic alkyl; or C6 or C10 aryl; 10a 10b 17 viii) –[C(R )(R )] OC(O)R ; wherein R is chosen from: a) C -C linear, branched, or cyclic alkyl; and 1 12 18a 18b b) –N(R )(R ); 18a 18b R and R are each independently hydrogen, C -C linear, 1 12 branched, or cyclic alkyl; or C or C aryl; 6 10 10a 10b 19 20 ix) –[C(R )(R )] NR C(O)R ; wherein R is chosen from: a) –H; and b) C -C linear, branched, or cyclic alkyl; wherein R is chosen from: a) C -C linear, branched, or cyclic alkyl; and 1 12 21a 21b b) –N(R )(R ); 21a 21b R and R are each independently hydrogen, C -C linear, 1 12 branched, or cyclic alkyl; or C or C aryl; 6 10 10a 10b x) –[C(R )(R )] CN; 10a 10b xi) –[C(R )(R )] NO ; 10a 10b 22 xii) –[C(R )(R )] SO R ; R is hydrogen, hydroxyl, C -C linear or branched alkyl; C , C , or 1 4 6 10 C aryl; C -C alkylenearyl; C -C heterocyclic; or C -C 14 7 15 1 9 1 11 heteroaryl; and xiii) halogen; 10a 10b xiv) –[C(R )(R )] (CH X ) CH X ; wherein X is halogen, the index j y j’ k’ h j k is an integer from 0 to 2, the index k is an integer from 1 to 3, j + k = 3; the index j’ is an integer from 0 to 2, the index k’ is and integer from 0 to 2, j’ + k’ = 2; the index h is from 0 to 5; 10a 10b R and R are each independently hydrogen or C -C alkyl; and the index y is from 0 to 5; R and R can be taken together to form a 6 member ring containing from 4 to 6 carbon atoms and from 0 to 2 heteroatoms chosen from oxygen, sulfur, or nitrogen, wherein one or more of the carbon atoms can be a carbonyl unit; wherein R to R are each hydrogen.
16. A article according to Claim 16, wherein R and R are each independently chosen from: i) C -C linear, branched, or cyclic alkyl, alkenyl, and alkynyl; 1 12 ii) C -C linear, branched, or cyclic alkoxy, alkenyloxy, and alkynyloxy; 1 12 iii) C -C linear, branched, or cyclic haloalkyl, haloalkenyl, and haloalkynyl; 1 12 iv) C or C aryl; 6 10 v) C or C alkylenearyl; 6 10 102a 102b 101 vi) –(CR R ) OR ; 102a 102b 101 vii) –(CR R ) C(O)R ; 102a 102b 101 viii) –(CR R ) C(O)OR ; 102a 102b 101 ix) –(CR R ) C(O)N(R ) ; 102a 102b 101 x) –(CR R ) N(R ) ; xi) halogen; 102a 102b xii) –(CR R ) CN; 102a 102b xiii) –(CR R ) NO ; xiv) –CH X ; wherein X is halogen, the index j is an integer from 0 to 2, j + k = 102a 102b 101 xv) –(CR R ) SR ; 102a 102b 101 xvi) –(CR R ) SO R and 102a 102b 101 xvii) –(CR R ) SO R ; wherein each R is independently hydrogen, C -C linear, branched, or cyclic 102a 102b alkyl, phenyl, or benzyl; R and R are each independently hydrogen or C -C linear or branched alkyl; the index z is from 0 to 4.
17. The article according to Claim 15, wherein R and R can be taken together to from 6 member ring containing from 4 to 5 carbon atoms and 1 or 2 heteroatoms chosen from oxygen, sulfur, or nitrogen, wherein one or more of the carbon atoms is a carbonyl unit.
18. The article according to Claim 15, wherein the compound is chosen from: i) benzo[de]isochromen-1(3H)-one having the formula: ii) 1H-benzo[de]isoquinoline-1,3(2H)-dione having the formula: ; and iii) 2,3-dihydro-1H-benzo[de]isoquinolinone having the formula:
19. The article according to Claim 15, wherein the compound is benzo[de]- isochromene-1,3-dione having the formula:
20. The article according to Claim 15, wherein the compound has the formula: 1 8 14 R and R are each independently: –C(O)R ; 14 15 16a 16b 15 16a 16b wherein R is –OR or –N(R )(R ); R is hydrogen or methyl; R and R are each independently hydrogen or methyl.
21. The article according to Claim 15, wherein the compound is naphthalene-1,8- dicarboxamide having the formula:
22. The article according to Claim 15, further comprising from about 0.1% to about 10% by weight of an oxygen scavenger, wherein the oxygen scavenger is an N- allylic amide or N-benzylic amide.
23. The article according to Claim 15, wherein the base polymer comprises a polyester.
24. The article according to Claim 15, wherein the base polymer comprises polyethylene terephthalate or a copolymer thereof.
25. A polymer composition according to any one of Claims 1 to 11 substantially as herein described with reference to any example thereof and with or without reference to the accompanying figures.
26. A preform according to Claim 12 substantially as herein described with reference to any example thereof and with or without reference to the accompanying figures.
27. An article according to any one of Claims 13 to 24 substantially as herein described with reference to any example thereof and with or without reference to the accompanying figures.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161533449P | 2011-09-12 | 2011-09-12 | |
US61/533,449 | 2011-09-12 | ||
PCT/US2012/054840 WO2013040020A1 (en) | 2011-09-12 | 2012-09-12 | Monolayer carbon dioxide barrier pet bottles |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ623391A NZ623391A (en) | 2016-07-29 |
NZ623391B2 true NZ623391B2 (en) | 2016-11-01 |
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