EP4244261A1 - A method for preparing esterified cellulose and/or hemicellulose - Google Patents
A method for preparing esterified cellulose and/or hemicelluloseInfo
- Publication number
- EP4244261A1 EP4244261A1 EP21810058.4A EP21810058A EP4244261A1 EP 4244261 A1 EP4244261 A1 EP 4244261A1 EP 21810058 A EP21810058 A EP 21810058A EP 4244261 A1 EP4244261 A1 EP 4244261A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- anhydride
- hemicellulose
- cellulose
- mixture
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001913 cellulose Substances 0.000 title claims abstract description 155
- 229920002678 cellulose Polymers 0.000 title claims abstract description 153
- 229920002488 Hemicellulose Polymers 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 125
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 110
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 62
- 239000000194 fatty acid Substances 0.000 claims abstract description 62
- 229930195729 fatty acid Natural products 0.000 claims abstract description 62
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 62
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005886 esterification reaction Methods 0.000 claims abstract description 27
- 230000032050 esterification Effects 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 125000001924 fatty-acyl group Chemical group 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 125000002252 acyl group Chemical group 0.000 claims abstract description 13
- 239000003377 acid catalyst Substances 0.000 claims abstract description 10
- 235000010980 cellulose Nutrition 0.000 claims description 148
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 67
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229920001169 thermoplastic Polymers 0.000 claims description 20
- 239000004416 thermosoftening plastic Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002861 polymer material Substances 0.000 claims description 16
- 238000006467 substitution reaction Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 10
- 150000002190 fatty acyls Chemical class 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
- KLUDQUOLAFVLOL-UHFFFAOYSA-N acetyl propanoate Chemical compound CCC(=O)OC(C)=O KLUDQUOLAFVLOL-UHFFFAOYSA-N 0.000 claims description 4
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 238000010146 3D printing Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920002959 polymer blend Polymers 0.000 claims description 2
- 229920003124 powdered cellulose Polymers 0.000 claims description 2
- 235000019814 powdered cellulose Nutrition 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 239000002655 kraft paper Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 235000018185 Betula X alpestris Nutrition 0.000 description 7
- 235000018212 Betula X uliginosa Nutrition 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920005610 lignin Polymers 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 6
- 239000011121 hardwood Substances 0.000 description 6
- 238000004537 pulping Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000011122 softwood Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- -1 aliphatic monocarboxylic acid Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004137 mechanical activation Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 235000019737 Animal fat Nutrition 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 101710154526 Lytic chitin monooxygenase Proteins 0.000 description 2
- ADCQBLMDYBHFGK-UHFFFAOYSA-N acetyl octanoate Chemical compound CCCCCCCC(=O)OC(C)=O ADCQBLMDYBHFGK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- RAFYDKXYXRZODZ-UHFFFAOYSA-N octanoyl octanoate Chemical compound CCCCCCCC(=O)OC(=O)CCCCCCC RAFYDKXYXRZODZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- LYUPJHVGLFETDG-UHFFFAOYSA-N 1-phenylbutan-2-ol Chemical compound CCC(O)CC1=CC=CC=C1 LYUPJHVGLFETDG-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 244000283070 Abies balsamea Species 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 235000011624 Agave sisalana Nutrition 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 241000209763 Avena sativa Species 0.000 description 1
- 235000007558 Avena sp Nutrition 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241000219495 Betulaceae Species 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000014466 Douglas bleu Nutrition 0.000 description 1
- 244000004281 Eucalyptus maculata Species 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 101100286668 Mus musculus Irak1bp1 gene Proteins 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 240000001416 Pseudotsuga menziesii Species 0.000 description 1
- 235000005386 Pseudotsuga menziesii var menziesii Nutrition 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- 244000305267 Quercus macrolepis Species 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229940106135 cellulose Drugs 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- QFWZJBUYDUYIJQ-UHFFFAOYSA-M methylsulfinylmethane;tetrabutylazanium;fluoride Chemical compound [F-].CS(C)=O.CCCC[N+](CCCC)(CCCC)CCCC QFWZJBUYDUYIJQ-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- CVEMRMYVCNTJJV-UHFFFAOYSA-N propanoyl butanoate Chemical compound CCCC(=O)OC(=O)CC CVEMRMYVCNTJJV-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/20—Esterification with maintenance of the fibrous structure of the cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/14—Hemicellulose; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/14—Hemicellulose; Derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
Definitions
- the present disclosure relates to a method for preparing esterified cellulose and/or hemicellulose , to an esterified cellulose and/or hemicellulose and to a thermoplastic cellulose and/or hemicellulose polymer material .
- Cellulose and hemicellulose are renewable raw materials well suited for producing thermoplastic materials .
- Cellulose and/or hemicellulose may be homogeneously esterified e . g . using ionic liquids or solvents such as DMAC-LiCl or TBAF-DMSO, but they may be toxic and challenging to recycle , thereby making them less desirable for sustainable production in an industrial scale .
- Heterogeneous esterification approaches may also involve the use of solvents , such as acetic acid, which may contribute significantly to waste generated by the esterification process .
- a method for preparing esterified cellulose and/or hemicellulose is disclosed .
- the method may comprise mixing an anhydride mixture and cellulose and/or hemicellulose , thereby obtaining an esterification mixture , such that the anhydride mixture esterifies the cellulose and/or hemicellulose at least partially, thereby forming the esterified cellulose and/or hemicellulose ; and wherein the anhydride mixture is obtainable or obtained by
- the initial anhydride mixture comprises a mixed anhydride having a fatty acyl group and a shortchain acyl group, a portion of the short-chain acid anhydride , a short-chain acid and optionally a fatty acid anhydride having two fatty acyl groups ;
- Fig . 1 schematically illustrates an embodiment of the esterification process .
- a method for preparing esterified cellulose and/or hemicellulose is disclosed .
- the method may comprise mixing an anhydride mixture and cellulose and/or hemicellulose , thereby obtaining an esterification mixture , such that the anhydride mixture esterifies the cellulose and/or hemicellulose at least partially, thereby forming the esterified cellulose and/or hemicellulose ; and wherein the anhydride mixture is obtainable or obtained by
- the initial anhydride mixture comprises a mixed anhydride having a fatty acyl group and a shortchain acyl group, at least a portion of the shortchain acid anhydride , a short-chain acid and optionally a fatty acid anhydride having two fatty acyl groups ;
- the initial anhydride mixture may thus comprise at least a portion of the short-chain acid anhydride and/or at least a portion of the fatty acid ( s ) that have not reacted .
- the reacting the fatty acid with the shortchain acid anhydride in the presence of the acid catalyst , such that the initial anhydride mixture is obtained, and the removing of the short-chain acid, the short-chain acid anhydride and optionally water and/or impurities present in the initial anhydride mixture at least partially from the initial anhydride mixture , thereby obtaining the anhydride mixture may be referred to as production of reactive fatty acids or production of the anhydride mixture in the context of this specification .
- the by-products of the production of the anhydride mixture (the short-chain acid and the short-chain acid anhydride ) may be removed from the initial anhydride mixture and reused in subsequent production of the anhydride mixture and/or valori zed as a product .
- the short-chain acid and/or the short-chain acid anhydride removed at least partially from the initial anhydride mixture may be reused in the method or as a separate product . Additionally or alternatively, it may be possible to extract unreacted components from the initial anhydride mixture ( or from the anhydride mixture ) .
- the short-chain acid anhydride removed at least partially from the initial anhydride mixture may be partially reused in the method and/or partially removed from the method .
- I f components removed at least partially from the initial anhydride mixture are reused, they may also contain water, so that each reuse cycle may generate more water and/or other impurities in the method . Thus a part of the removed components may be directed out of the process . Any useful components may be utili zed for other suitable purposes , including those not mentioned in this specification .
- the initial anhydride mixture obtained comprises a mixed anhydride ( acetic octanoic anhydride ) , a portion of the short-chain acid anhydride ( acetic anhydride ) that has not reacted, a short-chain acid ( acetic acid) , a fatty acid anhydride ( octanoic anhydride ) and a portion of the fatty acid ( octanoic acid) that has not reacted .
- acetic octanoic anhydride a mixed anhydride
- acetic anhydride a portion of the short-chain acid anhydride that has not reacted
- acetic acid acetic acid
- octanoic anhydride a fatty acid anhydride
- octanoic acid octanoic acid
- acetic acid and acetic anhydride may be removed or separated e.g. by vacuum distillation or by any other suitable method described in this specification to obtain the anhydride mixture that may be used for the esterification.
- distillation at a temperature of at least 140 °C may readily remove the acetic acid and acetic anhydride (and possibly also e.g. residual water) from the initial anhydride mixture, such that the acetic octanoic anhydride and the octanoic anhydride remain in the anhydride mixture.
- Scheme 2 shows an exemplary schematic of the reaction mechanism in the esterification. Although cellulose is depicted in the scheme, a skilled person will understand that similar reaction mechanisms may apply to hemicellulose or a mixture thereof .
- R alkyl of long chain faty acids
- the fatty acyls of the mixed anhydride may react with hydroxyl groups ( -OH) of the cellulose and/or hemicellulose , such that covalent ester bonds are formed .
- the short-chain acyls of the mixed anhydride ( and optionally of the short-chain acid anhydride ) may react with hydroxyl groups of the cellulose and/or hemicellulose .
- the removal of the short-chain acid and the short-chain acid anhydride at least partially from the initial anhydride mixture may increase the relative proportion of the mixed anhydride , a higher DS of the fatty acyl groups may be obtained than without it .
- thermoplastic cellulose and/or hemicellulose polymer material with desired properties , such as flowability and/or tensile strength .
- desired properties such as flowability and/or tensile strength .
- the need to add plastici zers to the thermoplastic cellulose and/or hemicellulose polymer material may be reduced .
- An extrudable thermoplastic cellulose and/or hemicellulose polymer material may also be obtained .
- the esterification may be performed as a one- pot reaction, i . e . in a single reactor .
- removing the short-chain acid, the short-chain acid anhydride and optionally water and/or impurities present in the initial anhydride mixture at least partially from the initial anhydride mixture , thereby obtaining the anhydride mixture may also be performed in a separate unit , for example in a separate distillation unit .
- the short-chain acid, short-chain acid anhydride , and/or the optional impurities may be at least partially removed by various different methods , including various separation and/or fractionation methods . This may enrich or increase the relative proportion of the mixed anhydride in the anhydride mixture . Thereby the degree of substitution of the fatty acyl ( s ) in the esterified cellulose and/or hemicellulose may be increased relative to the degree of substitution of the short-chain acyls .
- the impurities that may be at least partially removed may include e . g . possible degradation and/or side products of chemicals used in the method, and/or impurities from the chemicals used in the method .
- the short-chain acid, short-chain acid anhydride , and/or the optional impurities may have boiling points lower than the boiling points of the mixed anhydride and of the optional fatty acid anhydride .
- the short-chain acid, short-chain acid anhydride , and/or the optional impurities may be removed at least partially by a method capable of separating and/or fractionating compounds based on their boiling points . Examples of such methods may include e . g . distillation, vacuum distillation, and/or vacuum evaporation .
- the distillation may be performed at normal pressure ( ambient atmospheric pressure ) .
- Other methods that may be contemplated may include e . g .
- the short-chain acid, short-chain acid anhydride , and/or the optional impurities may be fractionated into two or more fractions .
- the proportion of the short-chain acid, short-chain acid anhydride , and/or the optional impurities that may be at least partially removed may depend e.g. on the proportion of the short-chain acid anhydride and other components in the initial anhydride mixture. For example, up to about 40 %
- short-chain acid may be understood as referring to a carboxylic acid having a shorter chain than the fatty acid(s) .
- short-chain acid anhydride may be understood as an anhydride of the short-chain acid, or of two short-chain acids, having a shorter chain than the fatty acid(s) .
- Suitable short-chain anhydrides may include e.g. formic anhydride (boiling point (bp) 92 °C) ; acetic formic anhydride; acetic anhydride (bp 138-140 °C) ; acetic propanoic anhydride (bp approx. 154 °C) ; propanoic anhydride (bp 167-170 °C) ; butanoic propanoic anhydride; and/or butanoic anhydride.
- formic anhydride tilting point (bp) 92 °C
- acetic formic anhydride acetic anhydride
- acetic anhydride bp 138-140 °C
- acetic propanoic anhydride bp approx. 154 °C
- propanoic anhydride bp 167-170 °C
- butanoic propanoic anhydride butanoic propanoic anhydride
- the short-chain acid anhydride may be represented by formula I wherein each Rx is independently selected from a C1-C4 alkyl.
- each R 1 may be the same (for example, both Rx groups in Formula I may be Cx alkyls, C2 alkyls, C3 alkyls or C4 alkyls) or they may be different. Each Rx may thus be independently selected from a Cx alkyl, a C2 alkyl, a C3 alkyl or a C4 alkyl.
- the mixed anhydride may be represented by formula II
- Rx is a C1-C4 alkyl
- R2 is an aliphatic chain having at least 4 carbon atoms, with the proviso that R 1 has fewer carbon atoms than R 2 .
- Rx may thus be selected from a Cx alkyl, a C2 alkyl, a C3 alkyl or a C4 alkyl .
- the optional fatty acid anhydride having two fatty acyl groups may be represented by formula III
- each R2 is independently selected from an aliphatic chain having at least 4 carbon atoms .
- hort-chain acid may be represented by
- Rx is a Cx ⁇ C4 alkyl.
- Rx may thus be selected from a Cx alkyl, a C2 alkyl, a C3 alkyl or a C4 alkyl .
- the fatty acid(s) and/or the fatty acyl group (s) of the mixed anhydride and of the optional fatty acid anhydride may, in principle, be any fatty acid(s) , including any aliphatic monocarboxylic acid, for example those derived from or contained in esterified form in an animal or vegetable fat, oil or wax .
- the fatty acid(s) and/or the fatty acyl group (s) of the mixed anhydride and of the optional fatty acid anhydride may be linear or branched. They may be saturated or unsaturated. Branched fatty acid(s) may reduce hydrogen bonding between cellulose and/or hemicellulose strands and may thereby help in obtaining easily plasticized cellulose and/ or hemicellulose .
- a fatty acid may, at least in some embodiments, refer to two or more fatty acids, and/or to a mixture of fatty acids. Therefore any references to "a fatty acid” or “the fatty acid” in this specification may, alternatively or additionally, be understood as references to two or more fatty acids, and/or to a mixture of fatty acids.
- the fatty acid(s) may be derived from e.g. a vegetable oil, animal fat, and/or tall oil. Typically such sources may provide a mixture of fatty acids having various compositions. It may be possible e.g. to distil out fatty acids of certain chain lengths and/or other properties and provide such fatty acids for use in the method.
- the fatty acid(s) and/or the fatty acyl group (s) of the mixed anhydride and of the optional fatty acid anhydride may each have 4 to 28 (i.e. 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, or 28) carbon atoms. In certain embodiments, they may have 6 to 20 carbon atoms, or 6 to 16 carbon atoms, or 8 to 16 carbon atoms. The number of carbon atoms may be understood as including the carbon atom of the carboxyl group of the fatty acid/fatty acyl group.
- each R2 may be independently selected from an aliphatic chain having 4 to 28 i.e. 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, or 28) carbon atoms. In certain embodiments, each R2 may be independently selected from an aliphatic chain having 6 to 20 carbon atoms, or 6 to 16 carbon atoms, or 8 to 16 carbon atoms.
- Reactivity of fatty acids may decrease upon increase in the number of carbon atoms; for example, fatty acids having more than 16 carbon atoms may have a lower reactivity.
- fatty acids having longer chains may allow for producing thermoplastic cellulose and/or hemicellulose polymer materials from the esterified cellulose and/or hemicellulose, even in embodiments in which the degree of substitution (DS) is lower.
- a skilled person may therefore select suitable fatty acid(s) and/or number (s) of carbon atoms such that the reactivity and/or the properties of the end product are desirable.
- the 4 to 28 carbon atoms, or any other number (s) of the carbon atom(s) , of the fatty acyl group (s) may be understood as including the carbon atom of the carboxyl group. In other words, the fatty acyl group (s) may then include 4 to 28 carbon atoms in total .
- the short acid anhydride may, at least in some embodiments, be selected from the group of formic anhydride, acetic anhydride, propionic anhydride, acetic propionic anhydride, and any mixtures and combinations thereof. These short acid anhydrides may have boiling points and/or other properties well suited for removing them at least partially from the initial anhydride mixture.
- the short acid anhydride may, at least in some embodiments, be selected from the group of acetic anhydride, propionic anhydride, acetic propionic anhydride, and any mixtures and combinations thereof.
- the short acid anhydride may, at least in some embodiments, comprise or be acetic anhydride.
- cellulose and/or hemicellulose may be understood as referring to cellulose; to hemicellulose; and/or to any mixture or combination thereof.
- it may refer to a mixture or composition comprising cellulose and optionally hemicellulose, such as pulp.
- Such a mixture may comprise predominantly cellulose, but also an amount of hemicellulose .
- pulp may typically contain e . g . about 10 - 25 % (w/w) of hemicellulose ; the remaining pulp may be cel lulose , although the pulp may additionally comprise impurities such as lignin residues ( typically less than 1 % (w/w) ) , extractives , and/or ash .
- hemicellulose may also be used instead of cellulose , or a mixture comprising predominantly hemicellulose and optionally cellulose .
- hemicellulose obtainable from textile processes may be contemplated .
- the cellulose and/or hemicellulose may, in some embodiments , be understood as referring to a composition comprising cellulose and/or hemicellulose and optionally one or more impurities , for example one or more of the impurities mentioned above .
- the cellulose and/or hemicellulose may be modified prior to the esterification .
- the cellulose and/or hemicellulose that is mixed with the anhydride mixture may already be modified .
- Various modifications may be available to cellulose and/or hemicellulose and may be compatible with the esterification according to one or more embodiments described in this specification .
- the cellulose and/or hemicellulose may be modified so as to contain charged ( anionic, cationic, or both) groups prior to the esterification .
- the cellulose and/or hemicellulose may be dry and powdered cellulose and/or hemicellulose , such as dry and powdered chemical pulp, when mixed with the anhydride mixture .
- the cellulose and/or hemicellulose may be activated prior to mixing with the anhydride mixture .
- the activated cellulose and/or hemicellulose may optional ly be dried prior to mixing with the anhydride mixture .
- the cellulose and/or hemicellulose may require drying after the activation.
- the cellulose and/or hemicellulose may be physically activated.
- the cellulose and/or hemicellulose may be mechanically activated and optionally dried prior to mixing with the anhydride mixture.
- the cellulose and/or hemicellulose may, alternatively or additionally, be mechanically disintegrated and dry before it is mixed with the anhydride mixture.
- the mechanical activation may be done e.g. by grinding the cellulose and/or hemicellulose.
- the mechanical activation may comprise mechanically pre-treating the cellulose and/or hemicellulose e.g. by refining, using a hammer mill, and/or pulverizing the cellulose and/or hemicellulose e.g. by friction grinding or using a ball mill. This may increase the surface area of the cellulose and/or hemicellulose and possibly cut a portion of the fibers in the cellulose and/or hemicellulose; however, typically the polymer length is not significantly affected.
- the cellulose and/or hemicellulose may be chemically activated.
- the cellulose and/or hemicellulose may be chemically activated by using e.g. ionic liquids, hydrolysis, and/or alkaline extraction.
- the cellulose and/or hemicellulose may be enzymatically activated.
- the enzymatic activation may be done e.g. by using a lytic polysaccharide monooxygenase (LPMO) and/or an endoglucanase .
- LPMO lytic polysaccharide monooxygenase
- the activation may be done to improve access to hydroxyl groups of the cellulose and/or hemicellulose.
- the cellulose and/or hemicellulose may be prepared earlier and stored and/or obtained separately e.g. by purchasing from a supplier, or it may be mechanically or otherwise activated shortly before the esterification. It may be beneficial to use the mechanically activated cellulose and/or hemicellulose relatively shortly after the mechanical activation to optimize esterification results.
- the dry cellulose and/or hemicellulose may thus be in the form of a high surface area powder.
- the cellulose and/or hemicellulose may, additionally or alternatively, comprise or be Kraft pulp, for example never dried Kraft pulp. However, any chemical pulp, such as soda and/or sulfite pulp, may also be used.
- the cellulose and/or hemicellulose, such as pulp may be obtainable from wood or from non-wood materials.
- the cellulose and/or hemicellulose may be prepared from cellulose raw material of a plant origin. The raw material may be based on any plant material that contains cellulose and/or hemicellulose. The plant material may be, for example, wood.
- the wood may be from a softwood tree, such as spruce, pine, fir, larch, Douglas fir or hemlock, or from a hardwood tree, such as birch, aspen, poplar, alder, eucalyptus, oak, beech or acacia, or from a mixture of a softwood and a hardwood.
- a softwood tree such as spruce, pine, fir, larch, Douglas fir or hemlock
- a hardwood tree such as birch, aspen, poplar, alder, eucalyptus, oak, beech or acacia, or from a mixture of a softwood and a hardwood.
- the cellulose and/or hemicellulose is obtained from wood pulp.
- the cellulose and/or hemicellulose is obtained from hardwood pulp.
- the hardwood is birch.
- the cellulose and/or hemicellulose is obtained from softwood pulp.
- Non-wood material may be derived from agricultural residues, grasses or other plant substances such as straw, leaves, bark, seeds, hulls, flowers, vegetables or fruits from cotton, corn, wheat, oat, rye, barley, rice, flax, hemp, manila hemp, sisal hemp, jute, ramie, kenaf, bagasse, bamboo or reed.
- HW hardwood
- SW softwood
- different polysaccharide compositions may exist in the cellulose and/or hemicellulose.
- the cellulose may contain hemicelluloses and lignin in varying amounts, depending on plant source and pulping conditions .
- bleached birch pulp has a high xylose content ( 25% by weight ) and a negligible lignin content .
- Pulps are typically complex mixtures of different polysaccharide structures .
- the cellulose and/or hemicellulose may be formed by isolating cellulose and/or hemicellulose from a raw material that contains cellulose by chemical , mechanical , thermo-mechanical , or chemi-thermo- mechanical pulping processes , for example kraft pulping, sulfate pulping, soda pulping, organosolv pulping, and by conventional bleaching processes .
- the cellulose and/or hemicellulose may, in some embodiments , not contain substantial amounts of lignin, or it may contain only traces of lignin or non-detectable amounts of lignin . Thus al so the cellulose and/or hemicellulose may be essentially lignin-free .
- additional solvent may be understood as a solvent added to the esterification mixture in order for the esterification reaction to proceed, apart from the short-chain acid (which may, at least in some embodiments , be considered to be a solvent and/or function as a solvent in the esterification) .
- the method may optionally comprise workup washing, which may include washing with a solvent . This may be done to remove the unreacted fatty acid ( s ) and/or other unwanted components from the esterified cellulose and/or hemicellulose . Such unwanted components may be removed e . g . so that they do not cause of f-flavours or migrate to the surface when the esteri fied cellulose and/or hemicellulose and/or a thermoplastic cellulose and/or hemicellulose polymer material ( for example , a film) comprising or prepared from it are in contact with food products .
- the term "additional solvent” is not intended to include the solvent ( s ) used in the workup washing .
- the acid catalyst is not particularly limited . It may comprise or be a strong acid, such as sulfuric acid and/or hydrochloric acid . However, other acids and acid catalysts may also be contemplated .
- the anhydride mixture may be obtained, the cellulose and/or hemicellulose and the anhydride mixture may be mixed, and the cellulose and/or hemicellulose may be esterified in a single reactor . This may simpl ify the process and/or allow for easier scalability .
- the anhydride mixture and the cellulose and/or hemicellulose may be mixed and the anhydride mixture may esterify the cellulose and/or hemicellulose under mixing, for example under mechanical stirring or kneading .
- the mixing may result in a higher degree of substitution .
- the cellulose and/or hemicellulose may be optionally mechanically activated, the cellulose and/or hemicellulose and the anhydride mixture may be mixed, and the cellulose and/or hemicellulose may be esteri fied in a high consistency processing reactor .
- the mixing and kneading action that may be provided by the high consistency processing reactor may result in a higher degree of substitution of the esterified cellulose and/or hemicellulose ; it may thereby generate less waste than certain other approaches .
- the reagents may be circulated and reused .
- the esterified cellulose and/or hemicellulose obtained may be filtered and/or washed.
- the esterified cellulose and/or hemicellulose obtained may be dried, for example in an oven.
- the esterified cellulose and/or hemicellulose may then be used for various purposes, for example in the preparation of a thermoplastic cellulose and/or hemicellulose polymer material.
- An esterified cellulose and/or hemicellulose is also disclosed.
- the degree of substitution (DS) of fatty acyls in the esterified cellulose and/or hemicellulose may be greater than the DS of short-chain acyls in the esterified cellulose and/or hemicellulose.
- the total DS in the esterified cellulose and/or hemicellulose may be in the range of 0.2 to 3.0, wherein the DS of fatty acyls in the esterified cellulose and/or hemicellulose may be greater than the DS of short-chain acyls in the esterified cellulose and/or hemicellulose.
- the degree of substitution of fatty acyls in the esterified cellulose and/or hemicellulose may be, for example, at least 0.2, or in the range of 0.2 to 3.
- the degree of substitution of short-chain acyls in the esterified cellulose and/or hemicellulose may be up to 2.8, or in the range of 0.2 to 2.8) .
- the degree of substitution may be determined e.g. by nuclear magnetic resonance (NMR) methods .
- esterified cellulose and/or hemicellulose may be obtainable by the method according to one or more embodiments described in this specification.
- thermoplastic cellulose and/or hemicellulose polymer material is also disclosed.
- the thermoplastic cellulose and/or hemicellulose polymer material or thermoplastic cellulose and/or hemicellulose polymer mixture may comprise or be formed from the esterified cellulose and/or hemicellulose according to one or more embodiments described in this specification.
- thermoplastic cellulose and/or hemicellulose polymer material may further comprise various additives, such as e.g. a filler (for example, inorganic fine particles and/or organic compounds) , a plasticizer, a flame retardant, an antioxidant, a colouring (for example, a colouring pigment) , a masterbatch, etc.
- a filler for example, inorganic fine particles and/or organic compounds
- a plasticizer for example, a plasticizer
- a flame retardant for example, an antioxidant
- a colouring for example, a colouring pigment
- thermoplastic cellulose and/or hemicellulose polymer material may comprise up to 30 %, 0.1 - 30 % (w/w) , or up to 10 %, or 0.5 - 10 % (w/w) , or up to 5 % , or 0.1 - 5 % (w/w) of plasticizer (s) .
- esterified cellulose and/or hemicellulose may simply be purified and optionally e.g. extruded into a desired form (such as into grains or film) without adding further additives. Any additional components or the absence thereof may depend e.g. on the exact composition of the esterified cellulose and/or hemicellulose and/or the intended use thereof or of the thermoplastic cellulose and/or hemicellulose polymer material.
- the esterified cellulose and/or hemicellulose and/or the thermoplastic cellulose and/or hemicellulose polymer material may be extruded e.g. into grains, pellets, filaments, or a film or heat pressed to a film. Such films may be slightly transparent or transparent .
- An article obtainable from the esterified cellulose and/or hemicellulose according to one or more embodiments disclosed in this specification or from the thermoplastic cellulose and/or hemicellulose polymer material according to one or more embodiments disclosed in this specification is also disclosed.
- the article may be e.g. extruded, molded or heat pressed.
- the article may be e.g. a container, a casing, a packaging article, a film, a filmic label, a medical device (such as a nozzle) , a plastic or composite profile, or a 3D printing filament.
- a container e.g. a container, a casing, a packaging article, a film, a filmic label, a medical device (such as a nozzle) , a plastic or composite profile, or a 3D printing filament.
- FIG 1 schematically illustrates an embodiment of the esterification process.
- acetic anhydride as the short-chain acid anhydride a mixed anhydride having a fatty acyl group derived from the fatty acid and a short-chain acyl group (acetyl) derived from the short-chain acid anhydride.
- the resulting reactive fatty acid i.e.
- anhydride mixture is then subjected to a suitable separation procedure, for example distillation as shown in Scheme 1, such that at least a portion of the acetic acid and acetic anhydride remaining after the reaction are removed. They may be recycled back into the production of the reactive fatty acid at 1 as indicated by an arrow.
- the mixed anhydride remains in the anhydride mixture.
- At least a portion of impurities may also be removed in the separation procedure , as indicated by an arrow .
- water may be removed in the separation procedure (not shown in Fig . 1 ) .
- the acetic acid anhydride removed at least partially from the initial anhydride mixture may be partially reused in the method and/or partially removed out of the process , as shown by arrows .
- I f components removed at least partially from the initial anhydride mixture may also contain water, so that each reuse cycle may generate more water and/or other impurities in the method . Thus a part of the removed components may be directed out of the process .
- kraft pulp such as never dry kraft pulp
- the cellulose and/or hemicellulose source is activated, for example by mechanical grinding, and dried .
- the activated anhydride mixture containing the mixed anhydride , i . e . reactive fatty acid, from 1 is mixed with the activated cellulose and/or hemicellulose at 3 , such that the esterification reaction may proceed .
- the esterification reaction has proceeded to a sufficient extent , the resulting esterified cellulose and/or hemicellulose may be filtered and washed at 4 .
- the resulting thermoplastic cellulose and/or hemicellulose at 5 may be e . g . dried and optionally processed further or used as such e . g . by extruding it into a film or an article .
- the reactor temperature was lowered to at least 60 °C by using water cooling and then 1 1 of 50 % ethanol mixture was carefully poured into the reactor. This extraction took 30 min, and then the suspension was carefully poured into a 10 1 container.
- the product was filtered from the dilute acetic acid mixture, mixed with 4 1 of deionized water, washed with water, the procedure being repeated until washings with water gave neutral pH suspension. Water was removed as far as possible by filtration and then the product was dried in an oven at 105 °C.
- the pulp used in the examples contained, in addition to cellulose, about 25 % (w/w) of hemicellulose; less than 1 % (w/w) of lignin residues; 0.2 % (w/w) extractives; and 0.4 % (w/w) ash.
- the reactor temperature was lowered to at least 60 °C by using water cooling and then 1 1 of 50 % ethanol mixture was carefully poured into the reactor. This extraction took 30 min, and then the suspension was carefully poured into a 10 1 bucket or similar.
- the product was filtered from the dilute acetic acid mixture, mixed with 4 1 of deionized water, washed with water, the procedure being repeated until washings with water gave neutral pH suspension. Water was removed as far as possible by filtration and then the product was dried in an oven at 105 °C.
- Esterified cellulose was produced as described in Example 2, except a 6 h reaction was performed with a Juccheim reactor.
- This reactive fatty acid mixture was added to a batch reactor together with 0.5 g of sulfuric acid catalyst with mixing set to about 11 Hz and the temperature was raised to 80 °C.
- the reactor temperature was lowered to at least 60 °C by using water cooling, and then 1 1 of 50 % ethanol mixture was carefully poured into the reactor. This extraction took 30 min, and then the suspension was carefully poured into a 10 1 bucket or similar.
- the product was filtered from the dilute acetic acid mixture, mixed with 4 1 of deionized water, washed with ethanol and water, the procedure being repeated until washings with water gave neutral pH suspension . Water was removed as far as possible by filtration and then the product was dried in an oven at 105 ° C .
- This mixture was added to a reactor together with 1 mL of sulfuric acid catalyst with mixing set to about 40 rpm, and the temperature was raised to 80 ° C .
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