OA16693A - - Google Patents
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- Publication number
- OA16693A OA16693A OA1201400567 OA16693A OA 16693 A OA16693 A OA 16693A OA 1201400567 OA1201400567 OA 1201400567 OA 16693 A OA16693 A OA 16693A
- Authority
- OA
- OAPI
- Prior art keywords
- cellulose
- ether
- methyl
- acid
- hydroxyl groups
- Prior art date
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- 229920002678 cellulose Polymers 0.000 claims description 101
- 239000001913 cellulose Substances 0.000 claims description 98
- 239000000463 material Substances 0.000 claims description 86
- 239000000203 mixture Substances 0.000 claims description 77
- 239000002253 acid Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- -1 benzindazones Chemical class 0.000 claims description 22
- 235000013305 food Nutrition 0.000 claims description 20
- 230000035699 permeability Effects 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 229920000742 Cotton Polymers 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N Anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N Diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- KXKVLQRXCPHEJC-UHFFFAOYSA-N Methyl acetate Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- YFNKIDBQEZZDLK-UHFFFAOYSA-N Triethylene glycol dimethyl ether Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- DPBLXKKOBLCELK-UHFFFAOYSA-N Pentylamine Chemical class CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 7
- 150000001805 chlorine compounds Chemical class 0.000 claims description 7
- 230000000269 nucleophilic Effects 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 229920001046 Nanocellulose Polymers 0.000 claims description 5
- 235000013334 alcoholic beverage Nutrition 0.000 claims description 5
- 150000001649 bromium compounds Chemical class 0.000 claims description 5
- 235000020965 cold beverage Nutrition 0.000 claims description 5
- 235000012171 hot beverage Nutrition 0.000 claims description 5
- 150000004694 iodide salts Chemical class 0.000 claims description 5
- 150000002561 ketenes Chemical class 0.000 claims description 5
- 235000019520 non-alcoholic beverage Nutrition 0.000 claims description 5
- MZLKHPDPHGHSOY-UHFFFAOYSA-N (2,3-dioxoindole-1-carbonyl) 2,3-dioxoindole-1-carboxylate Chemical compound O=C1C(=O)C2=CC=CC=C2N1C(=O)OC(=O)N1C2=CC=CC=C2C(=O)C1=O MZLKHPDPHGHSOY-UHFFFAOYSA-N 0.000 claims description 4
- OVRRJBSHBOXFQE-UHFFFAOYSA-N 1,1,2,2-tetrabromoethene Chemical group BrC(Br)=C(Br)Br OVRRJBSHBOXFQE-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 4
- ARAFEULRMHFMDE-UHFFFAOYSA-N 1,3-oxazolidine-2,5-dione Chemical class O=C1CNC(=O)O1 ARAFEULRMHFMDE-UHFFFAOYSA-N 0.000 claims description 4
- RKIPCZGWRCITOW-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundecane Chemical class C1CCCCCCCCCC1N1CCCNCCCCCC1 RKIPCZGWRCITOW-UHFFFAOYSA-N 0.000 claims description 4
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 4
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2,6-dimethylheptan-4-one Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-Methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-Butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N 2-Pentanone Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- YGGRMHGSIHLAMS-UHFFFAOYSA-N ClNS=O Chemical class ClNS=O YGGRMHGSIHLAMS-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N DABCO Chemical class C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N Diethylene glycol diethyl ether Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N Diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N MeOtBu Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N Methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- XJRBAMWJDBPFIM-UHFFFAOYSA-N Methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 4
- 210000001724 Microfibrils Anatomy 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N Octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N Propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 240000000111 Saccharum officinarum Species 0.000 claims description 4
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N Sulfuryl chloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 4
- 210000003135 Vibrissae Anatomy 0.000 claims description 4
- 229940111121 antirheumatic drugs Quinolines Drugs 0.000 claims description 4
- 150000001539 azetidines Chemical class 0.000 claims description 4
- 150000001541 aziridines Chemical class 0.000 claims description 4
- 150000001556 benzimidazoles Chemical class 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M caproate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 4
- NBYQXBYMEUOBON-UHFFFAOYSA-N carbamothioyl chloride Chemical class NC(Cl)=S NBYQXBYMEUOBON-UHFFFAOYSA-N 0.000 claims description 4
- CKDWPUIZGOQOOM-UHFFFAOYSA-N carbamoyl chloride Chemical class NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001716 carbazoles Chemical class 0.000 claims description 4
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- 125000004925 dihydropyridyl group Chemical group N1(CC=CC=C1)* 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008079 hexane Substances 0.000 claims description 4
- WZELXJBMMZFDDU-UHFFFAOYSA-N imidazol-2-one Chemical class O=C1N=CC=N1 WZELXJBMMZFDDU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 150000002462 imidazolines Chemical class 0.000 claims description 4
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical class C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 claims description 4
- 150000002475 indoles Chemical class 0.000 claims description 4
- 150000002476 indolines Chemical class 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 150000002537 isoquinolines Chemical class 0.000 claims description 4
- 150000002545 isoxazoles Chemical class 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 150000002780 morpholines Chemical class 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000005054 naphthyridines Chemical class 0.000 claims description 4
- 150000004866 oxadiazoles Chemical class 0.000 claims description 4
- 150000002916 oxazoles Chemical class 0.000 claims description 4
- 150000002918 oxazolines Chemical class 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004885 piperazines Chemical class 0.000 claims description 4
- 150000003217 pyrazoles Chemical class 0.000 claims description 4
- 150000003222 pyridines Chemical class 0.000 claims description 4
- 150000003230 pyrimidines Chemical class 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- 150000003235 pyrrolidines Chemical class 0.000 claims description 4
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 4
- 150000003248 quinolines Chemical class 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 150000003536 tetrazoles Chemical class 0.000 claims description 4
- 150000004867 thiadiazoles Chemical class 0.000 claims description 4
- 150000003567 thiocyanates Chemical class 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 4
- 150000003219 pyrazolines Chemical class 0.000 claims description 3
- 150000003918 triazines Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 description 73
- 238000000576 coating method Methods 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 31
- 206010053317 Hydrophobia Diseases 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 6
- 125000005647 linker group Chemical group 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000001580 bacterial Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butanoic acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- WHTNHYRHHHFFBV-UHFFFAOYSA-N ClNS(=O)=O Chemical class ClNS(=O)=O WHTNHYRHHHFFBV-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000001419 myristoyl group Chemical group O=C([*])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 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 230000003000 nontoxic Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- LPWCRLGKYWVLHQ-UHFFFAOYSA-N tetradecanoyl chloride Chemical compound CCCCCCCCCCCCCC(Cl)=O LPWCRLGKYWVLHQ-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2R,3R,4S,5R,6S)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2S,3R,4S,5R,6R)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2R,3R,4S,5R,6R)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- HKQOBOMRSSHSTC-DIBAFDJWSA-N (2R,3S,4S,5R,6S)-2-(hydroxymethyl)-6-[(2R,3S,4R,5R,6R)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxane-3,4,5-triol;[(2R,3R,4S,5R,6S)-4,5,6-triacetyloxy-3-[(2S,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxyoxan-2-yl]methyl acetate;[( Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O)[C@H](O)[C@H]1O.CC(=O)OC[C@H]1O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1O[C@H]1[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1.CCC(=O)OC[C@H]1O[C@@H](OC(=O)CC)[C@H](OC(=O)CC)[C@@H](OC(=O)CC)[C@@H]1O[C@H]1[C@H](OC(=O)CC)[C@@H](OC(=O)CC)[C@H](OC(=O)CC)[C@@H](COC(=O)CC)O1 HKQOBOMRSSHSTC-DIBAFDJWSA-N 0.000 description 1
- VUKAUDKDFVSVFT-UHFFFAOYSA-N 2-[6-[4,5-bis(2-hydroxypropoxy)-2-(2-hydroxypropoxymethyl)-6-methoxyoxan-3-yl]oxy-4,5-dimethoxy-2-(methoxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)-5-methoxyoxane-3,4-diol Chemical compound COC1C(OC)C(OC2C(C(O)C(OC)C(CO)O2)O)C(COC)OC1OC1C(COCC(C)O)OC(OC)C(OCC(C)O)C1OCC(C)O VUKAUDKDFVSVFT-UHFFFAOYSA-N 0.000 description 1
- QOWAMIUFBNBINS-UHFFFAOYSA-N 2-[6-[4,5-diethoxy-2-(ethoxymethyl)-6-methoxyoxan-3-yl]oxy-4,5-dimethoxy-2-(methoxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)-5-methoxyoxane-3,4-diol Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(OC)C(OC)C(OC2C(C(O)C(OC)C(CO)O2)O)C(COC)O1 QOWAMIUFBNBINS-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N 289-95-2 Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- CWSZBVAUYPTXTG-UHFFFAOYSA-N 5-[6-[[3,4-dihydroxy-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxymethyl]-3,4-dihydroxy-5-[4-hydroxy-3-(2-hydroxyethoxy)-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxyoxan-2-yl]oxy-6-(hydroxymethyl)-2-methyloxane-3,4-diol Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OCCO)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 CWSZBVAUYPTXTG-UHFFFAOYSA-N 0.000 description 1
- 210000002421 Cell Wall Anatomy 0.000 description 1
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- 229920002301 Cellulose acetate Polymers 0.000 description 1
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
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- XAPRFLSJBSXESP-UHFFFAOYSA-N Oxycinchophen Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=C(O)C=1C1=CC=CC=C1 XAPRFLSJBSXESP-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- DQEFEBPAPFSJLV-WLTGXWPBSA-N [(2R,3R,4S,5R,6S)-4,5,6-tri(propanoyloxy)-3-[(2S,3R,4S,5R,6R)-3,4,5-tri(propanoyloxy)-6-(propanoyloxymethyl)oxan-2-yl]oxyoxan-2-yl]methyl propanoate Chemical compound CCC(=O)OC[C@H]1O[C@@H](OC(=O)CC)[C@H](OC(=O)CC)[C@@H](OC(=O)CC)[C@@H]1O[C@H]1[C@H](OC(=O)CC)[C@@H](OC(=O)CC)[C@H](OC(=O)CC)[C@@H](COC(=O)CC)O1 DQEFEBPAPFSJLV-WLTGXWPBSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2S,3R,4S,5R,6R)-2-[(2R,3R,4S,5R,6S)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2R,3R,4S,5R,6S)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001588 bifunctional Effects 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 229940110456 cocoa butter Drugs 0.000 description 1
- 235000019868 cocoa butter Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003433 contraceptive agent Substances 0.000 description 1
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002255 enzymatic Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
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- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001761 ethyl methyl cellulose Substances 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical group 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 235000015504 ready meals Nutrition 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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Description
METHODS FOR BIODEGRADABLE DERIVATIZATION OF CELLULOSIC SURFACES BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION [0001] The présent invention relates generally to methods of treating cellulosic-compound containing materials, and more specifically to methods of making cellulose-based materials more hydrophobie using a composition which esterifies available hydroxyl groupe, where such a composition is useful in modifying/coating surfaces of cellulose-based materials including packaging products.
BACKGROUND INFORMATION [0002] Cellulosic materials hâve a wide range of applications in industry as bulking agents, absorbents, and printing components. Their employment is preferred to that of other sources of material for their high thermal stability, good oxygen barrier function, and chemical/mechanical resilience (see, e.g., Aulin et al., Cellulose (2010) 17:559-574). Of great relevance is also the fact that these materials are fully biodégradable once dispersed in the environment, and that they are totally nontoxic. Cellulose and dérivatives thereof are the material of choice for environmentally friendly solutions in applications such as packaging for foodstuff and disposable goods.
[0003] The many advantages of cellulose are nonetheless countered by the hydrophilicity of the material, which shows a high affinity for water and are easily hydrated (see, e.g., Aulin et al., Langmuir (2009) 25(13):7675-7685). While this is a benefit for applications such as absorbents and tissues, it becomes an issue when the safe packaging of watery material (e.g., foodstuffs) is required. Long term storage of food, especially ready made meals which contain a significant amount of water, is made problematic in cellulose trays as they would first become soggy and then uitimately dîsrupt under the hydration of their fibers.
[0004] This problem is usually addressed in the industry by coating the cellulose fiber with some kind of hydrophobie organic material, for example a resin or a polymer, which would physically shield the underlying hydrophilic cellulose from the water in the contents. Materials such as PVC are routinely used for this purpose and are physically attached (i.e., spray coated) on the surfaces to be treated.
[0005] A similar problem is encountered when sealing foodstuff in its container by means of a film. This film requires even more stringent properties than the container itself. On top of the résistance to mechanical stress, the film must be thin enough to be peeled off, should ideally be transparent, heat résistant, and impermeant to gases such as CO2and oxygen, non toxic, and hydrophobie. Again, plastic in the form of polymers and resin is the présent solution of the industry. [0006] The need to corne up with more environmentally friendly, as well as renewable, packaging solutions has cast a shadow over the use of plastic. New materials have been designed which are either derived from natural sources or semi-synthetic sources and therefore are renewable and/or biodégradable. Materials such as poly-lactic acid (PLA) and poly hydroxyalkanoate (PHA) are the présent golden standard for biodégradable plastics. However, they suffer the drawbacks of heat instability and water sensitivity which severely limit their use in the packaging industry. It would be désirable to design a coating which is both heat résistant and hydrophobie, without sacrificing biodegradability.
SUMMARY OF THE INVENTION [0007] The présent disclosure relates to methods of treating cellulosic materials, including treating cellulose-containing materials with a composition that provides increased hydrophobicity while maintaining biodegradability of the cellulosic components. The methods as disclosed provide for estérification of available hydroxyl groups on cellulose and do not require the use of Lewis acids or separate catalysts to convert said hydroxyls to esters, where such hydroxyl groups are masked by bulky organic chains. The coating may be applied to pre-formed materials.
[0008] In embodiments, a method for treating a surface of a cellulose-containing (or cellulosic) material is disclosed including applying to the surface a composition containing an alkanoic acid derivative having the formula (I) or (II):
R-CO-X Formula (I)
X-CO-R-CO-X, Formula (II), [0009] where R is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon radical having from 6 to 50 carbon atoms, and where X and Xi are independently Cl, Br, or O(CO)OR, wherein when the alkanoic acid derivative comprises formula (II) X or Xt is the same or different; a base, and a first solvent, heating the applied composition on the surface; rinsing the surface with a second solvent; and drying the rinsed surface; where the composition esterifies at least a portion of the hydroxyl groups available via the cellulose ofthe material.
[0010] In one aspect, the cellulose-containing material exhibits greater hydrophobicity relative to the cellulose-containing material without the treatment.
[0011] In one aspect, the base is organic. In a related aspect, the organic base includes aziridines, azetidines, piperazines, piperidînes, pyridines, bipyridines, terpyridines, dihydropyridines, morpholines, N-alkylmorpholines, 1,4-diazabicyclo[2.2.2]octanes, 1,8 diazabicycloundecanes, 1,8-diazabicycloundecenes, dimethylated pentylamines, trimethylated pentylamines, pyrimidines, pyrroles, pyrrolidines, pyrrolidinones, indoles, indolines, indanones, benzindazones, imidazoles, benzimidazoles, imidazolones, imidazolines, oxazoles, isoxazoles, oxazolines, oxadiazoles, thiadiazoles, carbazoles, quinolines, isoquinolines, naphthyridines, triazines, triazoles, tetrazoles, triethylamines, pyrazoles, pyrazolines, and combinations thereof, [0012] In another aspect, the first and second solvents include pentane, hexane, heptane, octane, petroleum ether, naphtha, kerosene, petroleum, paraffin oil, benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, methylene chloride, chloroform, 1,2-dichloro-ethane, chlorobenzene, carbon tetrachloride, tetrabromoethylene, cyclopentane, cyclohexane, methylcyclohexane, anisole (methyl phenyl ether), tert-butyl methyl ether, dibenzyl ether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether, tetrahydrofuran, triisopropyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether (diglyme), diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 1,2-dimethoxyethane (DME, monoglyme), ethylene glycol monobutyl ether, triethylene glycol dimethyl ether (triglyme), triethylene glycol monomethyl ether, acetone, diisobutyl ketone, methyl n-propyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and combinations thereof.
[0013] In one aspect, the cellulose-based material comprises a cellulose selected from the group consisting of nanocellulose, cellulose nanofibres, whiskers or microfibril, microfibrillated or nanofibril cellulose, cotton or cotton blends, sugarcane cellulose, and combinations thereof. In a related aspect, the cellulose-based material includes a carton forfood storage, a shopping bag, eating utensîl, container for holding hot or cold beverages, cup, plate, a bag forfood storage, a bottle for carbonated liquid storage, a bottle for non-carbonated liquid storage, film forwrapping food, a garbage disposai container, a food handling implement, a fabric fibre (e.g., cotton or cotton blends), a water storage and conveying implement, a storage and conveying implement for alcoholic or non alcoholic drinks, an outer casing or screen for electronic goods, an internai or external piece of furniture, a curtain, upholstery, and combinations thereof.
[0014] In embodiments, a method for treating a surface of a cellulose-containing (or cellulosic) material is disclosed, including applying to the surface a composition containing a derivatizing agent which includes acid chlorides, acid bromides, acid iodides, anhydrides, ketenes, diketenes, chlorocarbolic acid esters, carbonic acid diesters, 2,5-diketooxazolidines, isatinic anhydride, isocyanates, carbamoyl chlorides, thiocyanates, thiocarbamoyl chlorides, sulfonyl chlorides, sulfonic acid anhydrides, N-chlorosulfonamides, suffi nie acid chlorides, N-chlorosulfinamides, and combinations thereof; a base; and a first solvent, heating the applied composition on the surface;
rinsing the surface with a second solvent; and drying the rinsed surface; where the resulting surface of the cellulose-based material exhibits a water contact angle of about 100°.
[0015] In a related aspect, the composition esterifies at least a portion of the hydroxyl groups available via the cellulose of the material, and the esterified hydroxyl groups are stable up to at least about 200° C. In one aspect, the esterified hydroxyl groups are stable at températures between about -100° C to about 250° C. In a further related aspect, the surface of the cellulosebased material exhibits a water contact angle of between about 60° to about 120°. In another related aspect, the surface treatment is chemically stable at températures of between about 200° C to about 250° C. In one aspect, the esterified hydroxyl groups are stable at températures between about -100° C to about 250° C. In another related aspect, the water vapor permeability of the treated surface is between about 10 Barrer units to about 20 Barrer units. In a further aspect, the oxygen permeability of the treated surface is between about 10 Barrer units to about 20 Barrer units. In another related aspect, the portion of the available hydroxyl groups on the cellulose surface which are esterified by the composition is between about 35 to about 40%, about 40% to about 50%, about 50% to about 60%, about 60 to about 70%, about 70% to about 80%, about 80% to about 90%, and about 90% to about 100%. In embodiments, the portion of the available hydroxyl groups is about 70%.
[0016] In embodiments, the compositions esterifies at least a portion of the hydroxyl groups available via the cellulose of the material with the dicarboxylic acid dérivative (see, e.g., linker of Formula (l)) to increase both mechanical and thermal stability. In one aspect, the esterified hydroxyl groups are stable at températures between about -100° C to about 300° C. In further related aspect, the surface of the cellulose-based material exhibits a water contact angle of between about 60° to about 120°. In another related aspect, the surface treatment is chemically stable at températures of between about 200° C to about 300° C.
[0017] In a related aspect, the composition crosslinks adjacent cellulose chains by estérification with both ends of a dicarboxylic acid dérivative (Formula (II)) to increase both mechanical and thermal stability. In one aspect, the esterified hydroxyl groups are stable at températures between about -100° C to about 300° C. In a further related aspect, the surface of the cellulose-based material exhibits a water contact angle of between about 60° to about 120°. In another related aspect, the surface treatment is chemically stable at températures of between about 200° C to about 300e C.
[0018] In embodiments, the composition applied to the cellulose-based (or cellulosic) material is a biodégradable product. In a related aspect, the product includes a carton forfood storage, a shopping bag, eating utensil, container for holding hot or cold beverages, cup, plate, a bag for food storage, a bottle for carbonated liquid storage, a bottle for non-carbonated liquid storage, film for wrapping food, a garbage disposai container, a food handling implement, a fabric fibre, a water storage and conveying implement, a storage and conveying implement for alcoholic or non alcoholic drinks, an outer casing or screen for electronic goods, an internai or external piece of furniture, a curtain and upholstery.
[0019] In embodiments, a method for treating a surface of a cellulose-containing (or cellulosic) material is disclosed including applying to the surface a composition containing an alkanoic acid dérivative having the formula (I) or (II):
R-CO-X Formula (I)
X-CO-R-CO-Xï Formula (II), [0020] where R is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon radical having from 6 to 50 carbon atoms, and wherein X and Xi are independently Cl, Br, or O(CO)OR; a base; and a first solvent, heating the applied composition on said surface; rinstng the surface with a second solvent; and drying the rinsed surface; where the resulting treated cellulose-containing material exhibits properties including a water contact angle of about 100°, is stable up to at least about 200° C, an oxygen permeability of less than about 10 Barrer units, a water vapour permeability of less than about 20 Barrer units, and combinations thereof.
BRIEF DESCRIPTION OF THE DRAWINGS [0021] Figure 1 shows an illustration of the surface of a cellulosic material before and after treatment as disclosed.
DETAILED DESCRIPTION OF THE INVENTION [0022] Before the présent composition, methods, and méthodologies are described, it is to be understood that this invention is not limited to particular compositions, methods, and experimental conditions described, as such compositions, methods, and conditions may vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting, since the scope of the présent invention will be limited only in the appended claims.
[0023] As used in this spécification and the appended claims, the singular forms a, an, and the include plural references unless the context cleariy dictâtes otherwise. Thus, for example, references to a derïvitizing agent includes one or more derivltizing agents, and/or compositions of the type described herein which will become apparent to those persons skilled in the art upon reading this disclosure and so forth.
[0024] Unless defined otherwise, ali technical and scientific terms used herein hâve the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Any methods and materials similar or équivalent to those described herein may be used in the practice or testing of the invention, as it will be understood that modifications and variations are encompassed within the spirit and scope of the instant disclosure.
[0025] It is well known that esters are organic molécules with a high biodegradability as bacterial enzymes readily break them down. They are however relatively stable to chemical agents such as heat.
[0026] In embodiments, the présent disclosure shows that by treating the surface of cellulose fibers with long chain alkanoic acid dérivatives the resulting surface is made strongly hydrophobie, as the cellulosic hydroxyl groups are masked by bulky organic chains (see, e.g., FIGURE 1). Moreover, if the alkanoic acid chain is bifunctional having two carboxyl groups at either end, the resulting diester can function as a crosslink between isolated cellulosic fibers and increase the thermal and mechanical résistance of the cellulosic fiber itself. These organic chains, once removed by bacterial enzymes, are easily digested as such. The derivatized surface displays a great deal of heat résistance, being able to withstand températures as high as 250° C and is obviously more impermeant to gases than the naked film underneath. The material is also transparent and résistant to mechanical damage as it is bound together by covalent bonding. In embodiments the material is semi-transparent, non-transparent and various colors. The material is therefore an idéal solution to the problem of derivatizing the hydrophilic surface of cellulose, in any embodiment in which cellulose materials may be employed.
[0027] As used herein, cellulosic means natural, synthetic or semisynthetic materials that can be molded or extruded into objects or films or filaments, which may be used for makîng such objects or films or filaments, that Is structurally and functionally similar to cellulose, e.g., coatings and adhesives (e.g., carboxymethylcellulose). In another example, cellulose, a complex carbohydrate (C6H10O5)n that is composed of glucose units, which forms the main constituent of the cell wall in most plants, is cellulosic.
[0028] As used herein, hydrophobicity means the property of being water-repellent, tending to repel and not absorb water.
[0029] As used herein, cellulose-containing material or cellulose-based material means a composition which consists essentially of cellulose. For example, such material may include, but is not limited to, a carton for food storage, a bag forfood storage, a shopping bag, eating utensil, container for holding hot or cold beverages, cup, plate, a bottle for carbonated liquid storage, a bottle for non-carbonated liquid storage, film forwrapping food, a garbage disposai container, a food handling implement, a fabric fibre (e.g., cotton orcotton blends), a water storage and conveying implement, alcoholic or non alcoholic drinks, an outer casing or screen for electronic goods, an internai or external piece of furniture, a curtain and upholstery.
[0030] As used herein, water contact angle means the angle measured through a liquid at which a liquid/vapor interface meets a solid surface. It quantifies the wettability of the solid surface by the liquid. The contact angle is a reflection of how strongly the liquid and solid molécules interact with each other, relative to how strongly each interacts with its own kind. On many highly hydrophilic surfaces, water droplets will exhibit contact angles of 0° to 30°. Generally, if the water contact angle is larger than 90°, the solid surface is considered hydrophobie.
I0 [0031] As used herein, water vapour permeability means breathability or a textile's ability to transfer moisture. There are at least two different measurement methods. One, the MVTR Test (Moisture Vapour Transmission Rate) in accordance with ISO 15496, describes the water vapor permeability (WVP) of a fabric and therefore the degree of perspiration transport to the outside air. The measurements détermine how many grams of moisture (water vapor) pass through a square meter of fabric in 24 hours (the higher the level, the higher the breathability).
[0032] As used herein, oxygen permeability means the degree to which a polymer allows the passage of a gas or fluid. Oxygen permeability (Dk) of a material is a function of the diffusivity (D) (i.e., the speed at which oxygen molécules traverse the material) and the solubility (k) (or the amount of oxygen molécules absorbed, per volume, in the material). Values of oxygen permeability 20 (Dk) typically fall within the range 10-150 x 10*11 (cm2 ml O2)/(s ml mmHg). A semî-logarithmic relationship has been demonstrated between hydrogel water content and oxygen permeability (Unit: Barrer unit). The International Organization for Standardization (ISO) has specified permeability using the SI unit hectopascal (hPa) for pressure. Hence Dk = 10-11 (cm2 ml O2) /(s ml hPa). The Barrer unit can be converted to hPa unit by multiplying it by the constant 0.75.
[0033] As used herein biodégradable, including grammatical variations thereof, means capable of being broken down especially into innocuous products by the action of living things (e.g., by microorganisms).
[0034] As used herein, neat means there is substantially no other molécule présent in the substance including the absence of a solvent.
[0035] The process as disclosed includes a one step reaction ïnvolving a solvent (e.g., toluene), an alkanoic acid dérivative (e.g., acid halide) and a base such as pyridine to be placed on a cellulosic-containing surface and heated, in embodiments, for a period of minutes to hours (it should be readily apparent to one of skill in the art that the time period and température used in the reaction may vary depending on the reactants and may be adjusted accordingly). In embodiments, any resulting gases are vented. The process as disclosed ensures that the hydroxyl groups on the surface are permanently attached (covalently linked) to the alkyl groups and may only be degraded by bacterial enzymatic intervention or very harsh acid or base extremes.
[0036] The acid dérivatives suitable for the practice of the présent invention are those having the general formula:
[0037] R-CO-X Formula (I) or X-CO-R-CO-X, Formula (II), [0038] wherein CO is the carbonyl group C=O, R is selected from straight-chain, branchedchain, or cyclic aliphatic hydrocarbon radicals having from about 6 to 50 carbon atoms and X and Xi independently represent the spécifie acid dérivative substituent, such as Cl, Br or O(CO)OR in case of anhydrides. In one aspect, X and Xi may be the same or different.
[0039] In embodiments, the linkers themselves may be linked in structures such as:
MFC-XrCO-R-CO-Xï-MFC Formula (III), [0040] wherein CO is the carbonyl group C=O, R is selected from straight-chain, branchedchain, or cyclic aliphatic hydrocarbon radicals having from about 6 to 50 carbon atoms and Xi and X2 represent the spécifie acid dérivative substituent, such as Cl, Br or O(CO)OR in case of anhydrides. In one aspect, Xi and X2 may be the same or different, wherein MFC is microfibrillated cellulose.
[0041] In other aspects, other linkers may include:
X—CO—R --CO-X! x — CO—R --CO — X,
X3 X4
Formula (IV) Formula (V), [0042] wherein CO is the carbonyl group C=O, R is selected from straight-chain, branchedchain, or cyclic aliphatic hydrocarbon radicals having from about 6 to 50 carbon atoms, and X, X^ X3, and X4 independently represent the spécifie acid dérivative substituent, such as Cl, Br or O(CO)OR in case of anhydrides. In one aspect, X, Xi,X3, and X4 may be the same or different.
[0043] In a related aspect, X3 and X4 represent dérivatives that may allow crosslinking to each other after the MFC has been modified by Xand X,.
[0044] In embodiments, the crosslinkers above may be used to conjugale a mixture of different celluloses, including the introduction of ligands that may allow crosslinking of said différence celluloses. In one aspect, the resulting mixture may provide more favorable physical or chemical properties to the surface. In another aspect, linkers may include:
X,—CO—Rt--CO—X2 r2 Formula (VI) [0045] wherein CO is the carbonyl group C=O, R, and R2 are independently selected from straight-chain, branched-chain, or cyclic aliphatic hydrocarbon radicals having from about 6 to 50 carbon atoms, and X1 and X2 independently represent the spécifie acid dérivative substituent, such as Cl, Br or O(CO)OR in case of anhydrides. In one aspect, Ri and R2 may be the same or different. In another aspect, R1 and R2 may be the same or different, wherein R2 comprises reactive groups that allow crosslinking to other R2 groups, Ri or to cellulose. In a related aspect, X1t and X2 may be the same or different.
[0046] In one aspect the cellulose material is pretreated to add additional OH groups to the cellulose surface which in turn are esterfied by the alkanoic acid dérivatives to increase mechanical and thermal stability as well increase tensile strength.
[0047] In embodiments, the compositions esterifies at least a portion of the hydroxyl groups available via the cellulose of the material with the dicarboxylic acid dérivative (see, e.g., linker of Formula (I)) to increase both mechanical and thermal stability. In one aspect, the esterified hydroxyl groups are stable at températures between about -100° C to about 300° C. In further related aspect, the surface of the cellulose-based material exhîbits a water contact angle of between about 60° to about 120°. In another related aspect, the surface treatment is chemically stable at températures of between about 200° C to about 300° C.
[0048] In embodiments, the compositions above crosslink adjacent cellulose chains by estérification with both ends of a dicarboxylic acid dérivative (see, e.g., linker of Formula (II)) to increase both mechanical and thermal stability. In one aspect, the esterified hydroxyl groups are stable at températures between about -100° C to about 300° C. In further related aspect, the surface of the cellulose-based material exhîbits a water contact angle of between about 60° to about 120°, In another related aspect, the surface treatment is chemically stable at températures of between about 200° C to about 300° C.
ΙΟ [0049] In embodiments, the method as disclosed may be used on any cellulose-based surface, including but not limited to, a film, a rigid container, a fabric or the like. In addition, the method may include the use of a carboxylic acid halide or analog (e.g., anhydride, ketenes and the like), a suitable nonprotic, non-nucleophilic solvent in which the reaction may proceed (e.g., toluene, xylene, dioxane, aliphatic and aromatic esters and esters) and a non-nucleophilic base to neutralize any evolved acidity (e.g., but not limited to, pyridine). In embodiments, the solvent may be brought to between about 100° C to abouti 20° C under stirring. The non-nucleophilic base, which may be présent at between about 5% to about 10% of the reaction volume, may be added to the acid halide, which acid halide may be présent at between about 5% to about 10%, whereby the combined materials (i.e., modifying mixture) above is ready to be applied to a cellulose-containing surface (i.e., the substrate). The substrate which may be dried prior to application (e.g., at about 100° C), may be treated with the modifying mixture by dipping, for example, and allowing the surface to be exposed to the mixture for about 2 minutes to about 5 minutes. The surface may then be removed from the mixture and rinsed with water or a hydro-polar organic solvent solution (e.g., 70% EtOH) to remove traces of the reactants, which solutions would be apparent to one of skill in the art. The substrate may be air dried or heated to dry the surface, after which the modified material is ready for use.
[0050] In general, it has been found that acyl groups containing fewer than about 6 carbon atoms in chain length do not produce satisfactory water-repellency. Accordingly, chain lengths greater than 6 carbon atoms may be used to practice the invention as disclsoed. In embodiments, chain lengths may be 8-50,10-40, and 10-30 carbon atoms. In embodiments, the carbon atom chain lenghth may be 10-20 carbon atoms. Exemplary of compounds wherein R (including R-i and/or R2) îs selected from aliphatic hydrocarbon radicals are caprylyl chloride, decanoyl chloride, lauroyl chloride, palmitoyl chloride and myristoyl chloride. Exemplary of compounds wherein R is selected from cyclic aliphatic hydrocarbon radicals is cyclohexanecarboxylic acid halide. Generally, however, straight-chain acyclic aliphatic acid halides or anhydrides may be used for this process as they are usually cheaper and more readily available, and also because the branched-chain and cyclic hydrocarbon radicals are not easily biodégradable. In some embodiments, it may be désirable to employ a mixture of two or more acid anhydrides, and such embodiments are within the scope of the présent disclosure. Also, acid bromides and acid iodides react in similar ways to the acid chlorides and may be substituted therefor. However, because the bromides and iodides are generally more expensive and less readily available, the équivalent acid chlorides may be used. For the practice of the présent methods, ordinary commercial grade acid chlorides hâve been found wholly suitable, the only necessary précaution being to prevent exposure of the easily hydrolyzable acid anhydrides to moisture.
[0051] In embodiments, acid dérivatives (or derivatizing agents) include acid chlorides, acid bromides, acid iodides, anhydrides, ketenes, diketenes, chlorocarbolic acid esters, carbonic acid diesters, 2,5-diketooxazolidines, isatinic anhydride, isocyanates, carbamoyl chlorides, thiocyanates, thiocarbamoyl chlorides, sulfonyl chlorides, sulfonic acid anhydrides, N-chlorosulfonamides, sulfinic acid chlorides, N-chlorosulfinamides, and combinations thereof. In embodiments, the amount of acid dérivative {or derivatizing agent) présent in the coating mixture is about 0.1 M to about 1M, abouti M to about 2M, in embodiments about 2M to about 3M, in embodiments about 0.1M to about 3M.
[0052] While not being bound by theory, thethickness ofthe coating as disclosed is independent ofthe amount of reagent, and instead relies on the length ofthe alkyl chain R, as there is no physical absorption of the coating on the substrate, but a chemical linktng reaction, which may be variable, on the hydroxyl layerofthe surface. Further, such reaction (i.e., estérification) may not be reiterated once the hydroxyl groups hâve reacted with the acid dérivative.
[0053] No spécial préparation ofthe material is necessary in practicing this invention, including that no Lewis acids or separate catalysts are required, except that the surface to be treated should be clean and free of dirt and excess moisture. In embodiments, normally air-dried material which contains a few percent adsorbed moisture may be used. In some embodiments, material may be dried prior to treatment (e.g., at about 100° C to about 110° C, for a few minutes) to remove most of the adsorbed moisture. The degree of water impermeability may be controlled by sélection ofthe thickness ofthe cellulose to be treated and also by varying the treatment conditions, in particular the acid dérivative selected, the concentration of acid dérivative in the reaction chamberand the duration of the exposure.
[0054] Depending on the source, the cellulose may be nanocellulose, cellulose nanofibres, whiskers or microfibril, microfibrillated, cotton or cotton blends, or nanofibril cellulose.
[0055] In embodiments, the amount of coating applied is sufficient to completely cover at least one surface of a cellulose-containing material. For example, in embodiments, the coating may be applied to the complété outer surface of a container, the complété inner surface of a container, or a combination thereof. In other embodiments, the complété upper surface of a film may be covered by the coating, or the complété under surface of a film may be covered by the coating, or a combination thereof. In some embodiments, the lumen of a device/instrument may be covered by the coating or the outer surface of the device/instrument may be covered by the coating, or a combination thereof. In embodiment, the amount of coating applied is sufficient to partially cover at least one surface of a cellulose-containing material. For example, only those surfaces exposed to the ambient atmosphère are covered by the coating, or only those surfaces that are not exposed to the ambient atmosphère are covered by the coating. As will be apparent to one of skill In the art, the amount of coating applied will be dépendent on the use of the material to be covered.
[0056] Any suitable coating process may be used to deliver any of the various coatings applied in the course of practicing this aspect of the method. In embodiments, coating processes include immersion, spraying, painting, and any combination of any of these processes, alone or with other coating processes adapted for practicing the methods as disclosed.
[0057] In general, longer chain acid dérivatives give greater impermeability, other factors such as depth of cellulose treated being equal. By increasing the concentration of acid dérivative, for example, to about one molar or increasing the exposure time, an acid dérivative may react more extensively with the cellulose being treated with the net resuit that again improved water-repellent characteristics are exhibited.
[0058] The invention correspondingly provides a method to achieve such coating by dissolving the modifying agent in a suitable solvent, such as a C4-C0 ether, ester, ketones, amides or nitriles, or aromatic compound such as xylene or toluene, alongside a non-nucleophilic base such as pyridine, to absorb the generated acid. The mixture is sprayed on the material to be derivatized and heated to about 100° C to about 115° C, 120° C to about 210° C or about 120° C to about 150° C for a variable period (e.g., for about 10 minutes to about 30 minutes, about 30 minutes to about an hour, about 1 hour to about 1,5 hours, about 2 to about 2.5 hours, from about 2.5 hours to about 3 hours or from about 2 hours to about 3 hours). The surface may then be rinsed with detergent (surfactant) and water or a solvent (e.g., acetone), or mixture thereof, and dried again. A surfactant may be an ionic (cationic and anionic) surfactant, a non-ionic surfactant, or a combination thereof.
[0059] Any suitable basic neutralization reagent may be used in accordance with the présent disclosure as long as the base is non-nucleophilic, so as not to react with the acid dérivative. In embodiments, suitable basic neutralization agents may include organic basic agents. Suitable basic agents may include monocyclic compounds and polycyclic compounds having at least one nitrogen atom, such as, for example, secondary amines, which include aziridines, azetidines, piperazines, piperidines, pyridines, bipyridines, terpyridines, dihydropyridines, morpholines, N-alkylmorpholines, 1,4-diazabicyclo[2.2.2]octanes, 1,8-diazabicycloundecanes, 1,8-diazabicycloundecenes, dimethylated pentylamines, trimethylated pentylamines, pyrimidines, pyrroles, pyrrolidines, pyrrolidinones, indoles, indolines, indanones, benzindazones, imidazoles, benzimidazoles, imidazolones, imidazolines, oxazoles, isoxazoles, oxazolines, oxadiazoles, thiadiazoles, carbazoles, quinolines, isoquinolines, naphthyridines, triazines, triazoles, tetrazoles, triethylamine, pyrazoles, pyrazolines, and combinations thereof. In embodiments, the monocyclic and polycyclic compounds may be unsubstituted or substituted at any carbon position on the ring. In embodiments, the amount of base présent in the coating mixture may be about 0.1 M to about 1M, about 1M to about 2M, about 2M to about 4M, about 0.1 M to about 3M, or about 0.1 M to about 5M. [0060] Suitable solvents include non-nucleophilic aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and petroleum ether, naphtha, kerosene, petroleum, paraffin oil, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, etc.; halogenated hydrocarbons, such as methylene chloride, chloroform, 1,2dichloro-ethane, chlorobenzene, carbon tetrachloride, tetrabromoethylene, etc.; alicyclic hydrocarbons, such as cyclopentane, cyclohexane, and, methylcyclohexane, etc.; ethers, such as anisole (methyl phenyl ether), tert-butyl methyl ether, dibenzyl ether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether, tetrahydrofuran, triisopropyl ether etc.; glycol ethers, such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether (diglyme), diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 1,2-dimethoxyethane (DME, monoglyme), ethylene glycol monobutyl ether, triethylene glycol dimethyl ether (triglyme), triethylene glycol monomethyl ether etc.; ketones, such as acetone, diisobutyl ketone, methyl n-propyl ketone; methyl ethyl ketone, methyl isobutyl ketone etc.; esters, such as methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate, etc.; carboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, etc. One or more of these compounds may be used, alone or in combination. In embodiments, the amount of solvent présent may be about 50% to about 99%, about 60% to about 95%, about 75% to about 90% (vol%).
[0061] It will be apparent to one of skill in the art that the sélection of cellulose to be treated, the acid dérivative reagent, the reaction température (or vapor pressure), and the exposure time are process parameters that may be optimized by routine expérimentation to suit any particular application for the final product.
[0062] In embodiments, among useful coating agents, such agents may include, but are not limited to, acid halides, acid anhydrides, esters, ketenes, diketenes, chlorocarbolic acid esters, carbonic acid diesters, 2,5-diketooxazolidines, isatinic anhydride, isocyanates, carbamoyl chlorides, thiocyanates, thiocarbamoyl chlorides, sulfonyl chlorides, sulfonic acid anhydrides, Nchlorosulfonamides, sulfinic acid chlorides, N-chlorosulfinamides.
[0063] The derivatized materials hâve altered physical properties which may be defined and measured using appropriate tests known in the art. For hydrophobicity the analytical protocol is the contact angle measurement, wherein a droplet of water is deposited on the surface and the angle of the interface measured using one of many commercial instruments available for the purpose, A spécifie standardized protocol to follow is defined by the American Society for Testing and Materials (protocol ASTM D7334 - 08).
[0064] The permeability of a surface to various gases such as water vapour and oxygen may also be altered by the coating process as the barrier function of the material is enhanced. The standard unit measuring permeability is the Barrer and protocols to measure these parameters are also available in the public domain (ASTM std F2476-05 for water vapour and ASTM std F2622-8 for oxygen), [0065] In embodiments, materials treated according to the presently disclosed procedure display a complété biodegradability as measured by the dégradation in the environment under microorganismal attack.
[0066] Various methods are available to define and test biodegradability including the shakeflask method (ASTM E1279 - 89(2008)) and the Zahn-Wellens test (OECD TG 302 B).
[0067] In embodiments, the derivatized surface may be characterized for various parameters pertaining to the newly formed water barrier function as set forth below;
) Degree of substitution. By comparing the dry weight of the derivatized item and the dry weight of the untreated substrate, the degree of substitution of the hydroxyl groups on the surface may be determined using the équation:
%S = (W2-Wi)/(MW - 1 - MWx)/Doh * 100, where W2 and W.| are the weight per unit area after and before treatment, respectîvely, MW isthe molecularweight ofthe derivatizing agent, MWx is the weight ofthe moiety attached to the C=O group in the molécule and DOh is the density of the hydroxyl groups on the cellulose surface. Typical results obtained by the methods described herein are in the range of about 60% to about 80% substitution, with a minimum requirement of about 50%.
2) Contact angle. The contact angle between a water droplet and the surface is an indicatorof hydrophobicity ofthe surface itself. It may be measured by standard techniques as recîted above. Typical results obtained by the methods as described herein are around 90°, with ranges of about 70° to about 110°.
3) Water vapor transmission rate (see above), which may be used to détermine water barrier function. The derivatization leads to an improvement of this parameter by at least two fold compared to a non-derivatized surface. Typical results obtained by the method as described herein are 670 g/m2 24h (compared to >1200 g/m2 24h for untreated surfaces).
4) Heat stability of barrier function. The barrier function is retained at températures up to about 200° C using the methods as described herein. This may be determined by heating triglycérides in a coated tray to said température and verifying the amount of absorption of the triglycérides onto the tray itself.
[0068] Materials suitable for treatment by the process of this invention include various forms of cellulose, such as cotton fibers, plant fibers such as flax, wood fibers, regenerated cellulose (rayon and cellophane), partially alkylated cellulose (cellulose ethers), partially esterified cellulose (acetate rayon), and other modified cellulose materials which have a substantial portion of their hydroxyl groups available for reaction. As stated above, the term cellulose includes ail of these materials and others of similar polysaccharide structure and having similar properties. Among these the relatively novel material microfibrillated cellulose (nanocellulose) (as defined e.g. in US patent US4374702 and application 20090221812, herein incorporated by référencé in their entiretîes) is particularly suitable for this application as it can form transparent films of high spécifie résistance. In other embodiments, celluloses may include but are not limited to, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose (cellulose nitrate), cellulose sulfate, celluloïd, methylcellulose, ethylcellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and combinations thereof.
[0069] The covalent modification/coating/cross-linking of the cellulose as disclosed, in addition to increasing its hydrophobicity, may also increase its tensile strength and flexibility, thereby further widening its spectrum of use. Ail biodégradable and partially biodégradable products made from or by using the modified cellulose disclosed in this application are within the scope of the disclosure.
[0070] Among the possible applications of the coating technology such items include, but are not limited to, containers for ail purpose such as boxes, trays, shopping bags, pipes and water conduits, food grade drsposable cutlery, plates and bottles, screens for TV and mobile devices, clothing (e.g., cotton or cotton blends) and medical devices to be used on the body or inside it such as contraceptives. Also, the coating technology as disclosed may be used on fumiture and upholstery, outdoors camping equipment and the like.
[0071] The following examples are intended to illustrate but not limit the invention.
EXAMPLES [0072] Example 1. Coating a thin transparent film made of microfibrillated cellulose (MFC).
[0073] The upper and lower surfaces of a thin transparent film made of microfibrillated cellulose (MFC) were treated with a composition comprising 1 ml of lauroyl chloride (neat) and 1 ml of pyridine (neat) in 20 ml of toluene (neat). After coating the surfaces of the film with the composition, the film was heated to about 110° C for about 3 hours. The sample was subsequently rinsed with acetone and dried. After drying, the sample was assessed for heat stability, water contact angle, and water vapor transmission rate (WVTR) test at 24 hours, 50° C and 50% RH.
[0074] The sample coating was chemîcally stable up to about 200° C, and showed a water contact angle of about 100°, which demonstrated that the material was now hydrophobie. The results of the water vapor transmission test showed superior barrier properties to the uncoated film, whose water permeability was off the instrument scale.
[0075] Example 2. Coating a food tray made of sugarcane cellulose.
[0076] A food tray of 15 cm by 20 cm in size was treated on its food contact (upper) surface with a composition comprising 10 ml of myristoyl bromide (neat) and 10 ml of triethylamine (neat) in 1000 ml of xylene (neat). After coating the surface(s) of the tray with the composition, the tray was heated to about 140° C for about 3 hours. The tray was subsequently rinsed with acetone and dried. After drying, the tray was assessed for heat stability, water absorption, triglycéride permeability and biodegradability.
[0077] The tray coating was chemically stable up to about 250° C, and showed no water absorption up to 30 days after treatment, while remaining fully biodégradable. The tray did not show any permeability to a suspension of triglycérides even after heating at températures above the smoke point for the fat (cocoa butter) itself.
(0078] Example 3. Tray coating degree of substitution [0079] Cellulose containing tray samples were eut into 3 cm2 areas, weighed, dried in a stove at about 100° C, then weighed agaîn. The samples were coated in 20 ml of dioxane plus 1ml of pyrimidine and 1 ml of myristoyl chloride, and refluxed for 10 minutes. Subsequently, the samples were washed in water:acetone, then dried again and weighed. Results are shown in Table 1.
Avg. moles/cm2 | Standard Déviation | |
Myristoyl* | 1.85e-005 | 8.33e-007 |
OH | 2.70e-005 | - |
* For myristoyl, substitution about 0.03 (i.e., about 3%).
[0080] Avg. degree of substitution of OH with the hydrophobie coating was determined to be about 0.68 (i.e., about 70%). See Table 2.
Sample | Tray Wt. | Dry Wt. | % Solid | Coat. Wt | Wt.of Coat | Moles | Area (cm2) | mol/cm2 | Deg. of Sub. |
Ctrl | 0.4964 | 0.4786 | 96.41 | - | - | - | - | - | - |
1 | 0.6379 | 0.6150 | 97.41 | 0.6373 | 0.0223 | 1.06e-004 | 6 | 1,76e-005 | 0.65 |
2 | 0.6856 | 0.6692 | 97.61 | 0.6919 | 0.0277 | 1.08e-004 | 6 | 1.79e-005 | 0.66 |
3 | 0.7257 | 0.7013 | 96.64 | 0.7257 | 0.244 | 1.16e-004 | 6 | 1.93e-005 | 0.71 |
4 | 0.7277 | 0.7029 | 96.59 | 0.7271 | 0.242 | 1,15e-004 | 6 | 1.91e-005 | 0.71 |
Avg. | 6 | 1,85e-005 | 0.68 | ||||||
Std. Dev. | - | 8.33e-007 | 0.03 |
[0081] Although the invention has been described with reference to the above examples, it will be understood that modifications and variations are encompassed within the spirit and scope of the invention. Accordingly, the invention is limited only by the following claims. Ail references disclosed 5 herein are hereby incorporated by reference in their entireties.
Claims (26)
- WHAT IS CLAIMED:1.A method for treating a surface of a cellulose-containing material comprising:applying to said surface a composition comprising:an alkanoic acid dérivative having the formula (I) or formula (II):R-CO-XFormula (I)X-CO-R-CO-X, (II) Formula (II) wherein R is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon radical having from 6 to 50 carbon atoms, and wherein X and Xi are independently Cl, Br, or 0(CO)OR, a base, and a first solvent;heating the applied composition on said surface;rinsing said surface with a second solvent; and drying said rinsed surface, wherein said composition esterifies at Ieast a portion of the hydroxyl groups available via the15 cellulose of the material.
- 2. The method of claim 1, wherein the cellulose-containing material exhibits greater hydrophobicity relative to the cellulose-containing material without said treating.20
- 3. The method of claim 1, wherein the base is non-nucleophilic.
- 4. The method of claim 3, wherein the base is organic.
- 5. The method of claim 4, wherein the organic base is selected from the group consisting of25 aziridines, azetidines, piperazines, piperidines, pyridines, bipyridines, terpyridines, dihydropyridines, morpholines, N-alkylmorpholines, 1,4-diazabicyclo[2.2.2]octanes, 1,8diazabicycloundecanes, 1,8-diazabicycloundecenes, dimethylated pentylamines, trimethylated pentylamines, pyrimidines, pyrroles, pyrrolidines, pyrrolidinones, indoles, indolines, indanones, benzindazones, imidazoles, benzimidazoles, imidazolones, imidazolines, oxazoles, isoxazoles,30 oxazolines, oxadiazoles, thiadiazoles, carbazoles, quinolines, isoquinolines, naphthyridines, triazînes, triazoles, tetrazoles, triethylamines, pyrazoles, pyrazolînes, and combinations thereof.
- 6. The method of claim 1, wherein the first and second solvents are selected from the group consisting of pentane, hexane, heptane, octane, petroleum ether, naphtha, kerosene, petroleum, paraffin oil, benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, methylene chloride, chloroform, 1,2-dichloro-ethane, chlorobenzene, carbon tetrachloride, tetrabromoethylene, cyclopentane, cyclohexane, methylcyclohexane, anisole (methyl phenyl ether), tert-butyl methyl ether, dibenzyl ether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether, tetrahydrofuran, triisopropyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether (diglyme), diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 1,2-dimethoxyethane (DME, monoglyme), ethylene glycol monobutyl ether, triethylene glycol dimethyl ether (triglyme), triethylene glycol monomethyl ether, acetone, diisobutyl ketone, methyl n-propyl ketone; methyl ethyl ketone, methyl isobutyl ketone, methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and combinations thereof.
- 7. The method of claim 1, wherein the cellulose-based material comprises a cellulose selected from the group consisting of nanocellulose, cellulose nanofibres, whiskers or microfibril, microfibrillated or nanofibril cellulose, sugarcane cellulose, cotton or cotton blends, and combinations thereof.
- 8. The method of claim 1, wherein the cellulose-based material is selected from the group consisting of a carton for food storage, a bag for food storage, a shopping bag, eating utensil, container for holding hot or cold beverages, cup, plate, a bottle for carbonated liquid storage, a bottle for non-carbonated liquid storage, film for wrapping food, a garbage disposai container, a food handling implement, a fabric fibre, a water storage and conveying implement, a storage and conveying implement for alcoholic or non alcoholic drinks, an outer casing or screen for electronic goods, an internai or external piece of furniture, a curtain, upholstery, and combinations thereof,
- 9. A method for treating a surface of a cellulose-containing material comprising: applying to said surface a composition comprising:a derivatizing agent selected from the group consisting of acid chlorides, acid bromides, acid iodides, anhydrides, ketenes, diketenes, chlorocarbolic acid esters, carbonic acid diesters, 2,5-diketooxazolidines, isatinic anhydride, isocyanates, carbamoyl chlorides, thiocyanates, thiocarbamoyl chlorides, sulfonyl chlorides, sulfonic acid anhydrides, Nchlorosulfonamides, sulfinic acid chlorides, N-chlorosulfinamides, and combinations thereof;a base, and a first solvent;heating the applied composition on said surface;rinsing said surface with a second solvent; and drying said rinsed surface, wherein the resulting surface of the cellulose-based material exhibits a water contact angle of about 100°.
- 10. The method of claim 9, wherein said composition esterifîes at least a portion of the hydroxyl groups available via the cellulose of the material, and wherein said esterified hydroxyl groupe are stable up to at least about 200° C.
- 11. The method of claim 10, wherein the portion of the available hydroxyl groups esterified on the surface of the cellulose of the material is greater than about 40%.
- 12. The method of claim 10, wherein the portion of the available hydroxyl groups esterified on the surface of the cellulose of the material greater than about 50%.
- 13. The method of claim 10, wherein the portion of the available hydroxyl groups esterified on the surface of the cellulose of the material is between about 60-90%.
- 14. The method of claim 9, wherein the base is selected from the group consisting of aziridines, azetidines, piperazines, piperidïnes, pyridines, bipyridines, terpyridines, dihydropyridines, morpholines, N-alkylmorpholines, 1,4-diazabicyclo[2.2.2]octanes, 1,8-diazabicycloundecanes, 1,8diazabicycloundecenes, dimethylated pentylamïnes, trimethylated pentylamines, pyrimidines, pyrroles, pyrrolidines, pyrrolidinones, indoles, indolines, indanones, benzindazones, imidazoles, benzimidazoles, imidazolones, imidazolines, oxazoles, isoxazoles, oxazolines, oxadiazoles,2l thiadiazoles, carbazoles, quinolines, isoquinolines, naphthyridines, triazines, triazoles, tetrazoles, triethylamines, pyrazoles, pyrazolines, and combinations thereof.
- 15. The method of claim 9, wherein the first and second solvents are selected from the group consisting of pentane, hexane, heptane, octane, petroleum ether, naphtha, kerosene, petroleum, paraffin oil, benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, methylene chloride, chloroform, 1,2-dîchloro-ethane, chlorobenzene, carbon tetrachloride, tetrabromoethylene, cyclopentane, cyclohexane, methylcyclohexane, anisole (methyl phenyl ether), tert-butyl methyl ether, dibenzyl ether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether, tetrahydrofuran, triisopropyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether (diglyme), diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 1,2dimethoxyethane (DME, monoglyme), ethylene glycol monobutyl ether, triethylene glycol dimethyl ether (triglyme), triethylene glycol monomethyl ether, acetone, diisobutyl ketone, methyl n-propyl ketone; methyl ethyl ketone, methyl isobutyl ketone, methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and combinations thereof.
- 16. The method of claim 9, where the cellulose-based material comprises a cellulose selected from the group consisting of nanocellulose, cellulose nanofibres, whiskers or microfibril cellulose, microfibrillated or nanofibril cellulose, sugarcane cellulose, cotton or cotton blends, and combinations thereof.
- 17. A product resulting from the process of claim 1, wherein the surface of the cellulose-based material exhibits a water contact angle of between about 60° to about 120°.
- 18. The product of claim 17, where the surface treatment is chemically stable up to températures of between about 200° C to about 300° C.
- 19. The product of claim 17, wherein the water vapour permeability of the treated surface is between about 10 Barrer units to about 20 Barrer units.
- 20. The product of claim 17, wherein the oxygen permeability of the treated surface is between about 10 Barrer units to about 20 Barrer units.
- 21. The product of claim 17, wherein the portion of the hydroxyl groups esterified on the surface of the cellulose-based material is greater than 40%.
- 22. The product of claim 17, wherein the portion of the hydroxyl groups esterified on the surface of the cellulose-based material is greater than 50%.
- 23. The product of claim 17, wherein the portion of the hydroxyl groups esterified on the surface ofthe cellulose-based material is between about 60-90%.
- 24. The product of claim 17, wherein the product is biodégradable.
- 25. The product of claim 17, wherein the product is selected from the group consisting of a carton for food storage, a bag forfood storage, a shopping bag, eating utensil, container for holding hot or cold beverages, cup, plate, a bottle for carbonated liquid storage, a bottle for non-carbonated liquid storage, film for wrapping food, a garbage disposai container, a food handling implement, a fabric fibre, a water storage and conveying implement, a storage and conveying implement for alcoholic or non alcoholic drinks, an outer casing or screen for electronic goods, an internai or external piece of furniture, a curtain, upholstery and combinations thereof.
- 26. A method for treating a surface of a cellulose-containing material comprising:applying to said surface a composition comprising:an alkanoic acid dérivative having the formula (I) or formula (II):R-CO-X Formula (I)X-CO-R-CO-X) Formula (II), wherein R is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon radical having from 6 to 50 carbon atoms, and wherein X and X1 are independently Cl, Br, orO(CO)OR;a base, and a first solvent, heating the applied composition on said surface;rinsing said surface with a second solvent; and drying said rinsed surface,5 wherein the resulting treated cellulose-containing material exhibits properties selected from the group consisting of a water contact angle of about 100°, is stable up to at least about 200° C, an oxygen permeability of less than about 10 Barrer units, a water vapour permeability of less than about 20 Barrer units, contains hydroxyl groups esterified on the surface of the cellulosecontaining material is greater than about 40%, and combinations thereof.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US13/531,939 | 2012-06-25 |
Publications (1)
Publication Number | Publication Date |
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OA16693A true OA16693A (en) | 2015-12-07 |
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