NZ623330B2 - Novel composition for preparing polysaccharide fibers - Google Patents
Novel composition for preparing polysaccharide fibers Download PDFInfo
- Publication number
- NZ623330B2 NZ623330B2 NZ623330A NZ62333012A NZ623330B2 NZ 623330 B2 NZ623330 B2 NZ 623330B2 NZ 623330 A NZ623330 A NZ 623330A NZ 62333012 A NZ62333012 A NZ 62333012A NZ 623330 B2 NZ623330 B2 NZ 623330B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- solution
- glucan
- poly
- nmmo
- water
- Prior art date
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 150000004676 glycans Polymers 0.000 title description 14
- 150000004804 polysaccharides Polymers 0.000 title description 14
- 229920001282 polysaccharide Polymers 0.000 title description 12
- 239000005017 polysaccharide Substances 0.000 title description 12
- 229920001503 Glucan Polymers 0.000 claims abstract description 68
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-Methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 230000001112 coagulant Effects 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000701 coagulant Substances 0.000 claims abstract description 10
- 229960000583 Acetic Acid Drugs 0.000 claims abstract description 7
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 54
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 14
- 150000002338 glycosides Chemical class 0.000 claims description 11
- 239000000243 solution Substances 0.000 description 78
- 239000007787 solid Substances 0.000 description 34
- 239000008103 glucose Substances 0.000 description 19
- 238000009987 spinning Methods 0.000 description 19
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 18
- 229960001031 Glucose Drugs 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 229920002678 cellulose Polymers 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 229920002892 amber Polymers 0.000 description 12
- 239000001913 cellulose Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000002609 media Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- ZTHYODDOHIVTJV-UHFFFAOYSA-N propyl 3,4,5-trihydroxybenzoate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 10
- 235000010388 propyl gallate Nutrition 0.000 description 10
- 108090000790 Enzymes Proteins 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N D-sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 8
- 229920002307 Dextran Polymers 0.000 description 8
- VGYYSIDKAKXZEE-UHFFFAOYSA-L Hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 8
- 229940075579 Propyl Gallate Drugs 0.000 description 8
- CZMRCDWAGMRECN-GDQSFJPYSA-N Sucrose Natural products O([C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O1)[C@@]1(CO)[C@H](O)[C@@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-GDQSFJPYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 239000000473 propyl gallate Substances 0.000 description 8
- 239000005720 sucrose Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- BJHIKXHVCXFQLS-UYFOZJQFSA-N Fructose Natural products OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910014033 C-OH Inorganic materials 0.000 description 5
- 229910014570 C—OH Inorganic materials 0.000 description 5
- -1 FeSO4 heptahydrate Chemical class 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 241000660147 Escherichia coli str. K-12 substr. MG1655 Species 0.000 description 4
- 239000007836 KH2PO4 Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- GNSKLFRGEWLPPA-UHFFFAOYSA-M Monopotassium phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 101700034878 setA Proteins 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- 241000194024 Streptococcus salivarius Species 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000004683 dihydrates Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- AVKUERGKIZMTKX-NJBDSQKTSA-N Ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 2
- AFYNADDZULBEJA-UHFFFAOYSA-N Bicinchoninic acid Chemical compound C1=CC=CC2=NC(C=3C=C(C4=CC=CC=C4N=3)C(=O)O)=CC(C(O)=O)=C21 AFYNADDZULBEJA-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229960000723 ampicillin Drugs 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M buffer Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
- 229920003013 deoxyribonucleic acid Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 150000004688 heptahydrates Chemical class 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- BPHPUYQFMNQIOC-NXRLNHOXSA-N isopropyl β-D-thiogalactopyranoside Chemical compound CC(C)S[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O BPHPUYQFMNQIOC-NXRLNHOXSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- SJRJJKPEHAURKC-UHFFFAOYSA-N n-methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000008057 potassium phosphate buffer Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000001954 sterilising Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- YTPMCWYIRHLEGM-BQYQJAHWSA-N 1-[(E)-2-propylsulfonylethenyl]sulfonylpropane Chemical compound CCCS(=O)(=O)\C=C\S(=O)(=O)CCC YTPMCWYIRHLEGM-BQYQJAHWSA-N 0.000 description 1
- GZCGUPFRVQAUEE-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L Ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 229940041514 Candida albicans extract Drugs 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L Dipotassium phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 241000282619 Hylobates lar Species 0.000 description 1
- 101710028361 MARVELD2 Proteins 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L Manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XHXUANMFYXWVNG-ADEWGFFLSA-N Menthyl acetate Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(C)=O XHXUANMFYXWVNG-ADEWGFFLSA-N 0.000 description 1
- 229910018890 NaMoO4 Inorganic materials 0.000 description 1
- XDIYNQZUNSSENW-ZCEBMVQDSA-N OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O XDIYNQZUNSSENW-ZCEBMVQDSA-N 0.000 description 1
- 229920000096 Plastarch material Polymers 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 125000000704 aldohexosyl group Chemical group 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000001747 exhibiting Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000001963 growth media Substances 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 230000002209 hydrophobic Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920003259 poly(silylenemethylene) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002731 protein assay Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate dihydrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 239000012064 sodium phosphate buffer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 210000001519 tissues Anatomy 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
-
- 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
- C08L5/02—Dextran; Derivatives thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
Abstract
Disclosed is a composition comprising N-methylmorpholine-N-oxide (NMMO), water, and poly(alpha(1-3) glucan) wherein the concentration of poly(alpha(1-3) glucan) is in the range of 5 - 20 % by weight with respect to the total weight of the solution, wherein the poly(alpha(1-3) glucan) is characterized by a number average molecular weight (Mn) of at least 10,000 Da; and, wherein the weight ratio of NMMO to water is in the range of 12 to 1.6. Also disclosed is a process of using said composition for preparing fibers, wherein the process comprises the steps of: dissolving poly(alpha(1-3) glucan) in a mixture of NMMO and water according to the composition defined above; causing said solution to flow through a spinneret forming a fiber; using a liquid coagulant (e.g., glacial acetic acid) to extract the NMMO from the thus formed fiber. d by a number average molecular weight (Mn) of at least 10,000 Da; and, wherein the weight ratio of NMMO to water is in the range of 12 to 1.6. Also disclosed is a process of using said composition for preparing fibers, wherein the process comprises the steps of: dissolving poly(alpha(1-3) glucan) in a mixture of NMMO and water according to the composition defined above; causing said solution to flow through a spinneret forming a fiber; using a liquid coagulant (e.g., glacial acetic acid) to extract the NMMO from the thus formed fiber.
Description
Novel Composition for Preparing Polysaccharide Fibers
This application is a PCT application and claims the benefit of priority
under 35 U.S.C. §119(e) to US. Provisional Patent Application Serial Number
61/543,423, filed on October 5, 2011, and US. Provisional Patent Application
Serial Number 61/543,428, filed October 5, 2011. The disclosures of the
foregoing ations are incorporated by reference in their entirety.
Field Of The Invention
The present invention is directed to a process for solution ng
poly(d(1—>3) glucan) from a solution thereof in a mixture of water and N-
morpholine-N-oxide, and to the solution itself. The poly(d(1—>3) glucan)
employed was synthesized by the action of an enzyme.
Background Of The Invention
Polysaccharides have been known since the dawn of civilization, primarily
in the form of cellulose, a polymer formed from glucose by natural processes via
B(1—>4) glycoside linkages; see, for example, Applied Fibre Science, F. Happey,
Ed., Chapter 8, E. Atkins, ic Press, New York, 1979. Numerous other
polysaccharide polymers are also disclosed therein.
Only cellulose among the many known polysaccharides has achieved
commercial prominence as a fiber. In ular, , a highly pure form of
lly occurring ose, is well-known for its beneficial attributes in textile
applications.
It is further known that cellulose exhibits sufficient chain ion and
backbone rigidity in solution to form liquid crystalline solutions; see, for e
O'Brien, US. Pat. No. 4,501,886. The ngs of the art suggest that sufficient
polysaccharide chain extension could be achieved only in B(1—>4) linked
polysaccharides and that any significant deviation from that backbone geometry
would lower the molecular aspect ratio below that required for the formation of an
ordered phase.
WO 52730
More recently, glucan polymer, characterized by d (1—>3) glycoside
linkages, has been isolated by contacting an aqueous solution of e with
thJ yltransferase ed from Streptococcus salivarius, Simpson et al.,
iology, vol 141, pp. 1451-1460 (1995). Highly crystalline, highly oriented,
low molecular weight films of d(1—>3)—D-glucan have been fabricated for the
purposes of x-ray diffraction analysis, Ogawa et al., Fiber ction Methods,
47, pp. 353-362 (1980). In Ogawa, the insoluble glucan polymer is acetylated,
the acetylated glucan dissolved to form a 5% solution in chloroform and the
solution cast into a film. The film is then subjected to stretching in ine at
150° C. which orients the film and stretches it to a length 6.5 times the original
length of the solution cast film. After stretching, the film is ylated and
crystallized by annealing in superheated water at 140° C. in a pressure vessel. It
is well-known in the art that exposure of polysaccharides to such a hot aqueous
environment results in chain cleavage and loss of molecular weight, with
concomitant degradation of mechanical properties.
Polysaccharides based on e and glucose itself are particularly
important e of their prominent role in photosynthesis and metabolic
processes. Cellulose and starch, both based on molecular chains of
polyanhydroglucose are the most abundant polymers on earth and are of great
commercial importance. Such polymers offer materials that are environmentally
benign throughout their entire life cycle and are constructed from renewable
energy and raw materials sources.
The term “glucan” is a term of art that refers to a polysaccharide
comprising -glucose monomer units that are linked in eight possible ways,
Cellulose is a glucan.
Within a glucan polymer, the repeating monomeric units can be linked in a
variety of configurations following an enchainment pattern. The nature of the
enchainment pattern depends, in part, on how the ring closes when an
aldohexose ring closes to form a hemiacetal. The open chain form ofglucose (an
aldohexose) has four tric centers (see below). Hence there are 24 or 16
possible open chain forms of which D and L glucose are two. When the ring is
closed, a new asymmetric center is created at 01 thus making 5 asymmetric
carbons. Depending on how the ring closes, for e, d(1—>4)—linked polymer,
e.g. starch, or B(1—>4)—linked polymer, e.g. cellulose, can be formed upon further
condensation to polymer. The configuration at C1 in the polymer determines
r it is an alpha or beta linked polymer, and the numbers in parenthesis
ing alpha or beta refer to the carbon atoms through which enchainment
takes place.
1 1
CH0 CH0
2 I =l= 2 I =l=
H—C—OH H—C—OH
HO—C—H HO—C—H
H—C—OH H—C—OH
I * 5 I =l=
H—C—OH HO—C—H
6 | 6 |
CHZOH CHZOH
D-Glucose L—Glucose
H OH H OH
(1-D Glucose [5-D Glucose
* asymmetric carbon center
The properties exhibited by a glucan polymer are determined by the
enchainment pattern. For e, the very different properties of cellulose and
starch are determined by the tive nature of their enchainment patterns.
Starch or amylose ts of d(1—>4) linked glucose and does not form fibers
among other things because it is swollen or dissolved by water. On the other
hand, cellulose consists of B(1—>4) linked glucose, and makes an excellent
structural material being both crystalline and hydrophobic, and is commonly used
for textile applications as cotton fiber, as well as for ures in the form of
wood.
Like other natural fibers, cotton has evolved under constraints wherein the
polysaccharide structure and physical properties have not been optimized for
textile uses. In particular, cotton fiber is of short fiber length, limited variation in
cross section and fiber fineness and is produced in a highly labor and land
intensive process.
n, US. Patent No. 7,000,000 discloses a process for preparing fiber
from liquid crystalline solutions of acetylated poly(d(1—>3) glucan). Thus thus
prepared fiber was then de-acetylated resulting in a fiber of poly(d(1—>3) glucan).
Summary Of The ion
Considerable benefit accrues to the process hereof that provides a highly
oriented and crystalline poly ((1093) glucan) fiber without sacrifice of molecular
weight by the on spinning of fiber from the novel solution hereof.
In one aspect the present ion is direct to a solution comprising N-
methylmorpholine-N-oxide (NMMO), water, and poly(d(1—>3) ) (PAG)
wherein the tration of poly(d(1—>3) glucan) is in the range of 5 — 20 % by
weight with respect to the total weight of the solution; and, wherein the weight
ratio of NMMO to water is in the range of 12 to 1.6.
In one embodiment, the solution is isotropic.
In another aspect, the t ion is directed to a process for
preparing a poly(alpha(193) glucan) fiber, comprising the steps of: dissolving in
a mixture of N-methylmorpholine-N-oxide (NMMO) and water, 5 to 20 % by
weight of the total weight of the resulting solution of poly(alpha(193) glucan)
(PAG) terized by a number average molecular weight (M) of at least
,000 Da, to form a solution, wherein the weight ratio of NMMO to water in said
solution is in the range of 12 to 1.6; causing said solution to flow through a
spinneret, g a fiber thereby, using a liquid coagulant to extract the NMMO
from the thus formed fiber.
In one embodiment, the solution is isotropic.
Brief ption Of The Drawing
is a tic diagram of an apparatus suitable for air gap or wet
spinning of liquid crystalline solutions of hexose polymer to form polysaccharide
Detailed Description
When a range of values is provided herein, it is intended to encompass
the end-points ofthe range unless specifically stated otherwise. Numerical
values used herein have the precision of the number of significant figures
ed, following the standard protocol in chemistry for significant figures as
outlined in ASTM E29-08 Section 6. For example, the number 40 encompasses
a range from 35.0 to 44.9, whereas the number 40.0 encompasses a range from
39.50 to 40.49.
The term “solids content” is a term of art. It is used herein to refer to the
percentage by weight of poly(d(1—>3) ) in the NMMO/water solution hereof.
It is calculated from the formula
Wt(G)
SC :
Wt(G) + Wt(NMMO) + Wt(Water)
where SC represents “solids content,” and Wt(G), O) and Wt(water) are
the respective weights of the poly(d(1—>3) glucan), the NMMO, and the water.
The term s content” is synonymous with the concentration by weight of
poly(d(1—>3) glucan) with respect to the total weight of solution.
Percent by weight is represented by the term “wt-%.”
While the term “glucan” refers to a polymer, it also asses
ers and low molecular weight polymers that are unsuitable for fiber
formation. For the purposes of the present invention, the polymer suitable for the
practice thereof shall be referred to as “poly(d(1—>3) glucan).”
A polymer, including glucan, and (1—>3) glucan) in particular, is
made up of a plurality of so-called repeat units covalently linked to one another.
The repeat units in a polymer chain are diradicals, the radical form providing the
chemical bonding between repeat units. For the purposes of the present
invention the term “glucose repeat units” shall refer to the diradical form of
glucose that is linked to other diradicals in the r chain, thereby forming
said r chain.
In one aspect, the present invention provides a solution comprising N-
methylmorpholine-N-oxide (NMMO), water, and poly(d(1—>3) glucan) (PAG)
wherein the tration of poly(d(1—>3) glucan) is in the range of 5 — 20 % by
weight with respect to the total weight of the solution; and, wherein the weight
ratio of NMMO to water is in the range of 12 to 1.6.
In one embodiment, the solution is isotropic.
For the purposes of the t invention, the term “isotropic solution”
refers to a on exhibiting a disordered morphology. Isotropic solutions stand
in contrast with the morphology of liquid crystalline solutions that exhibit ordered
regions as described in US. Patent 7,000,000. It has surprisingly been found
that the embodiment of the solution hereof that is isotropic is useful for the
preparation of fibers using common solution spinning methods such as are
known in the art.
The poly(d(1—>3) glucan) (PAG) suitable for use in the present invention is
a glucan characterized by Mn of at least 10,000 Da wherein at least 90 mol-% of
the repeat units in the polymer are glucose repeat units and at least 50% of the
linkages between glucose repeat units are (1(193) glycoside es.
Preferably at least 95 mol-%, most preferably 100 mol-%, of the repeat units are
glucose repeat units. ably at least 90 %, most preferably 100 %, of the
linkages between glucose units are (1(193) glycoside linkages.
The isolation and cation of various polysaccharides is described in,
for example, The Polysaccharides, G. O. ll, Vol. 1, Chap. 2, Academic
Press, New York, 1983. Any means for producing the d(1—>3) polysachharide
suitable for the invention in satisfactory yield and 90 % purity is suitable. In one
such method, disclosed in US. Patent 7,000,000, poly(d(1—>3)-D-glucose) is
formed by contacting an aqueous solution of sucrose with gth
glucosyltransferase isolated from Streptococcus salivarius according to the
methods taught in the art. In an alternative such method, the gth is generated by
genetically ed E. Coli, as described in detail, infra. .
The poly(d(1—>3) glucan) suitable for use in the present invention can
further comprise repeat units linked by a glycoside linkage other than q(1—>3),
including d(1—> 4), G(1—>6), B(1—>2), B(1—> 3), B(1—>4) or B(1—>6) or any
combination thereof. According to the t invention, at least 50% of the
glycoside linkages in the polymer are O(1—>3) ide linkages. Preferably at
least 90 %, most preferably 100 %, of the es between glucose units are
d(193) glycoside linkages.
According to the present invention, the ratio of NMMO to water on a
weight basis in the solution hereof is in the range of 12 to 1.6, as determined
from the formula:
ratio = (Wt. NMMO)/Wt. H20)
The solution hereof is prepared by combining NMMO, H20, and
poly(q(1—>3) glucan), agitating to obtain gh mixing. The amount of
poly(q(1—>3) glucan) in the solution ranges from 5 to 20 % by weight with respect
to the total weight of the solution. At concentrations of poly(q(1—>3) glucan)
below 5 % by weight, the fiber-forming capability of the on is greatly
degraded. Solution trations above 16 % by weight are increasingly
problematical to form. In the range of 16 to 20 % by weight, increasingly d
solution forming techniques are often required.
In one embodiment, the concentration of poly(q(1—>3) glucan) is in the
range of 10 to 15 % by weight.
In any given embodiment, the solubility limit of (1—>3) glucan) is a
function of the molecular weight, the NMMO/water ratio, the on of mixing,
the viscosity of the solution as it is being formed, the shear forces to which the
solution is subjected, and the temperature at which mixing takes place. In
general, lower molecular weight poly(q(1—>3) glucan) will be more soluble than
higher molecular , other things being equal. Generally, higher shear
mixing, longer mixing time, and higher temperature will be associated with higher
solubility. The m temperature for mixing is limited by the boiling point
and stability of the solvents. The optimum NMMO/water ratio may change
depending upon the other parameters in the mixing process.
In another aspect, the present invention is directed to a process for
preparing a poly(alpha(193) glucan) fiber, comprising the steps of: ving in
a mixture of N-methylmorpholine-N-oxide (NMMO) and water, 5 to 20 % by
weight of the total weight of the resulting solution of poly(alpha(193) glucan)
(PAG) characterized by a number e molecular weight (M) of at least
,000 Da, to form a ng solution, wherein the weight ratio of NMMO to
water in said solution is in the range of 12 to 1.6; causing said solution to flow
through a spinneret, forming a fiber thereby; and, using a liquid coagulant to
t the NMMO from the thus formed fiber. In one embodiment, the spinning
solution is isotropic.
While it is not strictly required in the practice of the invention, it is highly
desirable to combine the water and the NMMO before the addition of the glucan
polymer. The addition of water to NMMO lowers the melting point of the NMMO
to the point where it can be used safely without explosive decomposition.
In a further ment, the isotropic spinning solution further comprises
a poly(q(1—>3) glucan) wherein 100 % of the repeat units therein are glucose,
and 100 % of the linkages between glucose repeat units are ) glycoside
linkages.
The minimum solids content of poly(q(1—>3) glucan) required in the
ng solution in order to achieve achieve stable fiber formation varies
according to the specific molecular morphology and the molecular weight of the
2012/058850
poly(q(1—>3) ), as well as the NMMO/water ratio. It is found in the practice
of the invention that a 5% solids content is an imate lower limit to the
concentration needed for stable fiber formation. A solution having a solids
content of at least 10% is preferred. A solids content ranging from about 10% to
about 15% is more preferred . Preferred is a poly(alpha (193) glucan)
characterized by a number average molecular weight of ca. 50,000 to 70,000
Daltons. Optimum spinning performance for this particular polymer is achieved at
about 10 to about 12% solids content in a NMMO/water mixture wherein the
weight ratio of NMMO to water is in the range of 12 to 1.6.
Spinning from the NMMO/water solution can be accomplished by means
known in the art, and as described in O'Brien, op. cit. The viscous spinning
solution can be forced by means such as the push of a piston or the action of a
pump through a single or multi-holed spinneret or other form of die. The
ret holes can be of any cross-sectional shape, ing round, flat, multi-
lobal, and the like, as are known in the art. The extruded strand can then be
passed by ordinary means into a coagulation bath wherein is contained a liquid
coagulant which dissolves NMMO but not the polymer, thus causing the highly
ed polymer to coagulate into a fiber according to the present invention.
Suitable liquid coagulants include but are not limited to glacial acetic acid,
or NMMO/water mixtures characterized by a water concentration of at least 75 %
by weight. In one embodiment, the liquid coagulant is maintained at a
ature in the range of 20 — 100 0C
In one embodiment, the coagulation bath comprises acetic acid. It is
found in the practice of the invention that satisfactory results are achieved by
employing as the coagulant liquid an excess ofglacial acetic acid. During the
course of spinning, the l acetic acid absorbs both NMMO and water as the
as spun fiber passes through the ant bath.
Under some circumstances, a superior result is achieved when the
extruded strand first passes through an inert, noncoagulating layer, usually an air
gap, prior to introduction into the coagulation bath. When the inert layer is an air
gap, the spinning process is known as air-gap spinning. Under other
2012/058850
circumstances, extrusion directly into the coagulation bath is preferred, known as
wet-spinning.
Figure 1 is a schematic m of an apparatus suitable for use in the
fiber spinning process hereof. The worm gear drive, 1, drives a ram, 2, at a
controlled rate onto a piston, 3, fitted into a spinning cell, 4. The spinning cell, 4,
may contain filter assemblies, 5. A suitable filter assembly includes 100 and 325
mesh stainless steel screens. Another suitable filter assembly es a
Dynalloy X5, 10 micron sintered metal s, (Pall Corporation, Deland, FL). A
spin pack, 6, contains the spinneret and optionally stainless steel s as
prefilters for the spinneret. The extruded filament, 7, produced therefrom is
optionally directed through an inert non coagulating layer (typically an air gap)
and into a liquid coagulating bath, 9. The extrudate can be, but need not be,
directed back and forth through the bath between guides, 8 which are normally
fabricated of Teflon® PTFE. Only one pass through the bath is shown in Figure
1. On exiting the coagulation bath, 9, the thus ed filament, 11, can
optionally be directed through a drawing zone using independently driven rolls,
, around which the thus quenched filament is wound. The thus prepared
filament is then collected on plastic or ess steel bobbins using a wind up,
12, preferably provided with a traversing mechanism to evenly distribute the fiber
on the bobbin. In one embodiment, the process comprises a plurality of
independently driven rolls.
In one embodiment, a plurality of filaments is extruded through a multi-
hole spinneret, and the filaments so produced are converged to form a yarn. In a
further ment, the process further comprises a plurality of multi-hole
spinnerets so that a ity of yarns can be prepared simultaneously.
EXAMPLES
Materials
AL Description Vendor
Dialysis tubing Spectrapor 25225-226, 12000 VWR (Radnor, PA).
molecular weight cut-off
Sucrose 15 wt-% solids aqueous VWR.
solution (#BDH8029)
Dextran T-10 0) Sigma h.
l Undenatured (#459844) Sigma Aldrich
Antifoam Suppressor 7153 Cognis Corporation
(Cincinnati, OH).
N-methylmorpholine N NMMO Sigma Aldrich
Oxide
All other chemicals were obtained from commonly used suppliers of such
chemicals.
Molecular Weights
Molecular weights were determined by size exclusion chromatography
(SEC) with a GPCV/LS 2000TM (Waters Corporation, Milford, MA) chromatograph
equipped with two Zorbax PSM Bimodal-s silica columns (Agilent, Wilmington,
DE), using DMAc from J.T Baker, psburg, NJ with 3.0% LiCl (Aldrich,
Milwaukee, WI) as the mobile phase. Samples were dissolved in DMAc with
.0% LiCl. The degree of polymerization shown in Table 2 is based upon
number average lar weight.
Pre aration of lucos ltransferase th enz me
Seed medium
The seed medium, used to grow the starter cultures for the ters,
contained: yeast extract (Amberex 695, 5.0 grams per liter, g/L), K2HPO4 (10.0
g/L), KH2PO4 (7.0 g/L), sodium citrate dihydrate (1.0 g/L), (N H4)ZSO4 (4.0 g/L),
MgSO4 heptahydrate (1.0 g/L) and ferric ammonium citrate (0.10 g/L). The pH of
the medium was adjusted to 6.8 using either 5N NaOH or H2804 and the medium
was sterilized in the flask. Post sterilization additions included glucose (20 mL/L
of a 50% w/w solution) and ampicillin (4 mL/L of a 25 mg/mL stock solution).
Fermenter medium
The growth medium used in the fermenter contained: KH2PO4 (3.50 g/L),
FeSO4 heptahydrate (0.05 g/L), MgSO4 heptahydrate (2.0 g/L), sodium e
dihydrate (1.90 g/L), yeast t (Amberex 695, 5.0 g/L), Suppressor 7153
antifoam (0.25 milliliters per liter, mL/L), NaCl (1.0 g/L), CaC|2 dihydrate (10 g/L),
and NIT trace elements solution (10 mL/L). The NIT trace elements solution
contained citric acid monohydrate (10 g/L), MnSO4 hydrate (2 g/L), NaCl (2 g/L),
FeSO4 heptahydrate (0.5 g/L), ZnSO4 heptahydrate (0.2 g/L), CuSO4
pentahydrate (0.02 g/L) and NaMoO4 dihydrate (0.02 g/L). Post sterilization
ons included glucose (12.5 g/L of a 50% w/w solution) and ampicillin (4
mL/L of a 25 mg/mL stock solution).
Construction of lucos ltransferase th enz me ex ression strain
A gene encoding the mature glucosyltransferase enzyme (gth; EC
2.4.1.5; GENBANK® AAA26896.1, SEQ ID NO: 3) from Streptococcus salivarius
(ATCC 25975) was synthesized using codons optimized for expression in E. coli
(DNA 2.0, Menlo Park CA). The nucleic acid product (SEQ ID NO: 1) was
subcloned into pJexpress404® (DNA 2.0, Menlo Park CA) to te the
plasmid identified as pMP52 (SEQ ID NO: 2). The plasmid pMP52 was used to
transform E. coli MG1655 (ATCC 'V') to te the strain identified as
MG1655/pMP52. All procedures used for construction of the glucosyltransferase
enzyme expression strain are well known in the art and can be performed by
individuals skilled in the relevant art without undue experimentation.
Production of recombinant gth in fermentation
Production of the recombinant gth enzyme in a ter was initiated by
ing a pre-seed e of the E. coli strain MG1655/pMP52, expressing the
2012/058850
gth , constructed as described infra. A 10 mL aliquot of the seed
medium was added into a 125 mL disposable baffled flask and was inoculated
with a 1.0 mL culture of E. coli MG1655/pMP52 in 20% glycerol. This culture was
allowed to grow at 37 °C while shaking at 300 revolutions per minute (rpm) for 3
hours.
A seed culture, for starting the fermenter, was prepared by ng a 2 L
shake flask with 0.5 L of the seed medium. 1.0 mL of the ed culture was
aseptically transferred into 0.5 L seed medium in the flask and cultivated at 37 °C
and 300 rpm for 5 hours. The seed culture was transferred at optical density 550
nm (OD550) >2 to a 14 L fermenter (Braun, Perth Amboy, NJ) containing 8 L of
the fermenter medium described above at 37 °C.
Cells of E. coli MG1655/pMP52 were allowed to grow in the fermenter and
glucose feed (50% w/w glucose solution containing 1% w/w MgSO4'7H20) was
initiated when glucose tration in the medium decreased to 0.5 g/L. The
feed was started at 0.36 grams feed per minute (g feed/min) and increased
ssively each hour to 0.42, 0.49, 0.57, 0.66, 0.77, 0.90, 1.04, 1.21, 1.41
1.63, 1.92, 2.2 g feed/min respectively. The rate was held constant aftenNards
by decreasing or temporarily stopping the glucose feed when glucose
concentration exceeded 0.1 g/L. Glucose concentration in the medium was
monitored using a YSI glucose analyzer (YSI, Yellow Springs, Ohio).
ion of glucosyltransferase enzyme activity was initiated, when cells
d an OD550 of 70, with the addition of 9 mL of 0.5 M IPTG (isopropyl 8-D-
1-thiogalacto- pyranoside). The dissolved oxygen (DO) concentration was
controlled at 25% of air saturation. The DO was controlled first by impeller
agitation rate (400 to 1200 rpm) and later by aeration rate (2 to 10 standard liters
per minute, slpm). The pH was controlled at 6.8. NH4OH (14.5% /volume,
WM and H2804 (20% w/v) were used for pH control. The back pressure was
maintained at 0.5 bars. At various intervals (20, 25 and 30 hours), 5 mL of
Suppressor 7153 antifoam was added into the fermenter to suppress foaming.
Cells were harvested by centrifugation 8 hours post IPTG addition and were
stored at -80 0C as a cell paste.
Preparation of gth crude enzyme extract from cell paste
The cell paste obtained above was suspended at 150 g/L in 50 mM
potassium ate buffer pH 7.2 to prepare a . The slurry was
homogenized at 12,000 psi (Rannie-type machine, APV-1000 or APV 16.56) and
the homogenate chilled to 4 0C. With moderately vigorous stirring, 50 g of a floc
solution ch no. 409138, 5% in 50 mM sodium phosphate buffer pH 7.0) was
added per liter of cell homogenate. Agitation was reduced to light stirring for 15
minutes. The cell homogenate was then clarified by fugation at 4500 rpm
for 3 hours at 5-10 OC. atant, containing crude gth enzyme extract, was
trated (approximately 5X) with a 30 kilo Dalton (kDa) cut-off membrane.
The concentration of protein in the gftJ enzyme solution was determined by the
bicinchoninic acid (BCA) protein assay (Sigma Aldrich) to be 4-8 g/L.
EXAMPLES 1 — 3 AND COMPARATIVE EXAMPLES A - D
Examples 1 - 3
Polymer P1:
Twenty liters of an aqueous solution was prepared by combining 3000 g of
e (in the form of an aqueous solution of 15 wt-%), 60 g of Dextran T-10 2
L of undenatured ethanol, and 1 L of 1M KH2PO4.‘ The pH was adjusted to pH
6.8 — 7.0 by on of 10 % KOH. De-ionized water was then added to bring
the volume up to 20 L. The buffer concentration in the thus prepared solution
was 50 mM.
The thus prepared pH-adjusted solution was then charged with 200 ml of
the enzyme extract prepared supra, and allowed to stand at ambient temperature
for 144 hours. The resulting glucan solids were ted on a Buchner funnel
using a 325 mesh screen over 40 micron filter paper. The filter cake was re-
suspended in deionized water and filtered twice more as above to remove
sucrose, fructose and other low molecular weight, soluble by-products. Finally
two additional washes with methanol were carried out, the filter cake was
pressed out thoroughly on the funnel and dried in vacuum at room temperature.
The yield was 403 grams of white flaky solids. The r so prepared is
herein designated P1.
Number and weight e molecular weights were found to be 64,863
and 168,120 Daltons respectively.
-30 mg of the polymer were dissolved in 1mL of ated DMSO.
The 13c NMR spectrum (Bruker Avance 500 MHz NMR spectrometer equipped
with a CPDul cryoprobe) showed the presence of resonance peaks at 98.15,
73.57, 71.63, 70.17, 65.79 and 60.56, ppm due to incorporation of dextran primer
and resonances consistant with the six expected discrete carbon atoms for poly
(0t(193) glucan) at 99.46, 81.66, 72.13, 71.09, 69.66, and 60.30 ppm . These
nces were consistent with the presence of poly(0t(193) glucan)
containing about 5% dextran.
Pre aration of ol or 1—>3 lucan S innin Solution
In a drybox, a 100 mL wide mouth glass bottle was charged with 8 g of
Polymer P1, and 46 g of anhydrous ylmorpholine N oxide (NMMO). To
the mixture so-formed were added 21 g of deionized water containing 0.344g of
gallic acid propyl ester and 0.086 g of hydroxylamine sulfate. The container was
fitted with a cap through which a polypropylene stirring rod had been fitted
through a septum. The contents were then heated to 110 CC with intermittent
manual mixing performed for about 5 minutes every hour over a period of 6
hours. After 1 hour, vacuum was applied to remove water while the contents
continued to be mixed. After 6 hours, 0.6 g of water had been removed resulting
in a fiber-forming light amber on of 10.75 % poly(d(1—>3) glucan) solids that
could be extruded into fiber under the conditions shown below.
Pol 0i 1—>3 lucan Fiber 8 innin
The apparatus ed in Figure 1, as described supra, was modified by
removal of the driven roll, 10, from the filament pathway. Spin stretch was
attained by running the windup faster than the jet velocity. The spinning solution
thus ed was fed at a rate of 0.30 ml/min through a spin pack having a filter
assembly consisting of 100 and 325 mesh screens to a one hole spinneret with a
diameter of 0.003 in.. The extruded filament was passed through an air gap of
1.75 in. (Examples 1 and 2) or 0.75 in. (Example 3), before being immersed in
and traversing a 2.5 ft. long coagulation bath containing glacial acetic acid at the
temperature indicated in Table 1. Upon removal from the ation bath the
thus coagulated filament was ed to a tension-controlled p with a
traverse rod, at a wind-up speed shown in Table 1.
Physical properties such as tenacity, elongation and initial modulus were
measured using methods and instruments conforming to ASTM Standard D
2101-82, except that the test specimen length was one inch.
Table 1 shows the properties ofthe thus prepared nts. These
e the denier of the fiber produced, and the physical properties such as
tenacity (T) in grams per denier (gpd), elongation to break (E, %), and initial
modulus (M) in gpd were measured using methods and instruments conforming
to ASTM Standard D 2, except that the test specimen length was one
inch. s shown in Table 1 are averages for 3 to 5 individual filament tests.
Comparative es A — D
Preparation of cellulose spinning solution
In a drybox, a 100 ml wide mouth glass bottle was charged with 5g of
cellulose derived from shredded Whatman #1 filter paper and 54 g of anhydrous
NMMO. To the mixture so formed were added 7.6 g of deionized water
containing 0.13g of gallic acid propyl ester and 0.033 g of hydroxylamine sulfate.
The ner was fitted with a cap through which a polypropylene stirring rod
had been fitted through a septum. The contents were then heated to 115 CC with
occasional (5-10 minutes/hour) manual mixing over a period of 4 hours. At that
time dissolution was complete yielding a fiber-forming light amber solution at 7.5
% cellulose solids that could be extruded into fiber under the conditions shown
below.
Cellulose Fiber Spinning
Cellulose filaments were prepared using the apparatus and procedures
employed in Examples 1 - 3, as described supra, except that the feed rate of the
spinning solution to the spinneret was 0.2 ml/min, and the air gap was 1.25 in.
(Comparative Examples A - C) or 1.75 in. (Comparative Example D). The
ation bath was 4.8 ft. in length, and contained water only. The coagulated
cellulose fiber was wrapped around driven roll, 10, depicted in Figure 1. The
remaining ions are shown in Table 1.
al properties were determined as in es 1 — 3. Results are
shown in Table 1.
TABLE 1
BATH Jet Roll Wind-up T E M dpf
TEMP (C) Velocity Speed Speed (gpd) (%) (gpd)
Examples (fpm) (m/min) (fpm)
1 23 50 na 70 0.8 15.4 41.3 17.3
2 24 50 na 90 0.8 11.8 13.5 13.5
3 25 50 na 70 0.8 16.2 16.2 16.2
Comp.Ex. 10 30 22 30 1.5 4.2 97 23.1
Comp.Ex. 10 30 35 44 1.7 6.4 105 17.4
x. 11 30 49 50 1.4 8.8 84 15.5
Comp.Ex. 11 30 49 56 1.5 2.3 128 12.3
EXAMPLES 4 - 17 AND COMPARATIVE EXAMPLES E - M
PREPARATION OF SPINNING SOLUTIONS
Solubiliity Determination
Solubility was determined by visual inspection of the solution in the vial
after the dissolution process, described in the examples, infra, was complete. If
by visual inspection no les or haziness was observed, the poly(0I(1—>3)
WO 52730
glucan) was said to completely dissolved. Detection of any particles or haziness
was considered to be an indication of incomplete solubility.
From the standpoint of preparing solutions suitable for fiber spinning, the
homogeneity imparted by complete solubility is very highly preferred.
In the data tables, infra, solubility is indicated by “,”8 meaning completely
dissolved, or “,"N meaning not tely dissolved.
Polymer sis
Polymer P2
Three liters of an aqueous solution containing 15% sucrose, 9g of
Dextran T-10, 300 ml of undenatured ethanol, and 50 ml of 1 molar KH2PO4 pH
6.8 — 7.0, were combined in a vessel. The pH was adjusted with 10 % KOH,
and the volume brought up to 3 liters with de-ionized water. The solution was
then d with 20.1 ml (.67 volume per cent) enzyme ed supra and
d to stand at ambient temperature for 144 hours. The resulting glucan
solids were collected on a Buchner funnel using a 325 mesh screen over 40
micrometer filter paper. The filter cake was suspended in deionized water and
filtered twice more as above to remove sucrose, fructose and other low molecular
weight, soluble by products. Finally two additional washes with methanol were
carried out, the filter cake was pressed out on the funnel and dried in vacuum at
room temperature. Yield was 25.5 grams of white flaky solids. The polymer so
prepared is herein designated P2.
Three liters of an aqueous solution containing 15% sucrose, were
combined in a vessel with 9g of n T-10, 300 ml of undenatured ethanol,
and 150 ml of potassium phosphate buffer adjusted to pH 6.8 — 7.0 using 10
%KOH. The volume was brought up to 3 liters with deionized water. The
solution was then d with 30 ml (1 vol%) enzyme prepared supra and
allowed to stand at ambient temperature for 72 hours. The resulting glucan
solids were collected on a Buchner funnel using a 325 mesh screen over 40
micron filter paper. The filter cake was suspended in deionized water and filtered
twice more as above to remove sucrose, fructose and other low molecular
weight, soluble by products. Finally two onal washes with methanol were
carried out, the filter cake was pressed out on the funnel and dried in vacuum at
room temperature. Yield was 55.4 grams of white flaky solids. The polymer so
prepared is herein designated P3.
Glucan Primer
25 grams of ground polymer P3 was suspended in 500 ml of 37% HCI
(EMD HX0603-4) with a magnetic stir bar in a 500 ml eyer flask and
allowed to hydrolyze for 2 hours. The acid was neutralized slowly using NaOH
solids with 50 ml of water added to keep the hydrolyzed glucan in solution while
being cooled in an ice bath. The solution was then dialyzed using 500 MW cut
off membrane (Specta/Por Biotech Cellulose Ester (CE) MWCO 500-1,000D)
with tap water flowing at a low level overnight to remove salts. The solution was
then placed in a p, and the al was dried under vacuum at room
temperature. The material so prepared is herein designated P3-H
The materials and procedures employed for preparing polymer P1 were
repeated except that 4.6 g of P3-H was employed, and the Dextran was omitted.
The polymer so prepared is herein designated P4. Yield was 309 grams of white
flaky .
In a 150 gallon glass lined reactor with stirring and temperature control
approximately 394kg of an aqueous solution was prepared by ing in a
vessel 75 kg of sucrose, 500 g of Dextran T-10, 3.4 kg of potassium phosphate
buffer ed to pH 7.0 using 10 % KOH, and 50 liters of undenatured ethanol.
The solution was then charged with 32 units/liter of enzyme prepared supra
followed by an additional 1 liter of de-ionized water. The ing solution was
mixed mildly at 25 °C for 72 hours. The resulting glucan solids was transferred to
a Zwag filter with the mother liquor d. The cake was washed via
displacement with water 3 times with approximately 150 kg of water. Finally two
additional displacement washes with 100 liters of methanol were carried out.
The material was dried under vacuum with a 60 °C jacket. Yield: 6.6 kg white
flaky solids. The polymer thus prepared is herein ated P5
The materials and procedures for preparing r P3 were replicated
except that 2.0 g of P3-H were employed and the Dextran was omitted. Yield
was 68 grams of white flaky solids. The polymer so prepared is herein
designated P6.
Example 4
0.5 g of Polymer P2 was added to a mixture formed by combining of 8g of
a 50/50 by weight mixture of anhydrous NMMO and water with 0.15 ml of an
aqueous solution of propyl gallate (0.08M) and hydroxylamine sulfate (0.026 M).
The thus combined ingredients were charged to a 40 ml glass vial. After
charging, the vial was capped with a silicone septum and the vial was d.
The septum was then fitted with a stirring rod. The vial was placed into a heating
block preheated to 110 oC and kept there for 30 minutes with occasional manual
stirring. After 30 minutes, vacuum was applied while continuing to heat at 110 °C
to remove water to the level shown in Table 2. Final water content was
determined by weighing the amount that was led off. Distillation of NMMO
was negligible. The polymer was fully dissolved and was light amber in color.
Final solids content was 8.9%.
Example 5
1.0 g of r P4 was ded in 8.5 g of a 50/50 by weight mixture
of anhydrous NMMO and water, to which was added 0.15 ml of an aqueous
solution of propyl gallate (0.016M) and hydroxylamine sulfate (0.005 M). The
ingredients were charged into a 40 ml glass vial fitted with a silicone septum.
After ng the vial, its contents were weighed. A ng rod was then
inserted through the septum. The vial was then placed into a heating block
preheated to 110 oC and held there for 60 minutes with occasional manual
stirring. After 60 minutes, vacuum was applied while heating at 110 °C was
continued, to remove water to the level shown Table 2. The r was fully
dissolved and was light amber in color. Final solids t was 8.1 wt-%.
Example 6
8.0 g of polymer P1 was suspended in a mixture containing 46 g
anhydrous NMMO, and 21 ml of an aqueous solution of propyl gallate (0.08M)
and hydroxylamine sulfate (0.026 M) . The ingredients were charged into a 100
ml wide d glass vial. After charging, the vial was capped with a
septum/stirrer and the assembly was weighed. The mixture was then heated at
110 CC for 30 minutes with occasional manual mixing. After 30 minutes vacuum
was d while continuing to heat at 110 CC to remove water to the level
shown in Table 2. The polymer was fully dissolved and light amber in color.
Final solids content was 10.9%.
Comparative e E
The materials and procedures of Example 6 except that 10.0 g of polymer
P1 was suspended in the NMMO/aqueous solution mixture. The polymer was not
fully dissolved. Final solids content was 13.7%.
Comparative Example F
The materials and procedures of Example 6 were reproduced except that
the NMMO/HZO ratio was ed to a different value as shown in Table 2. The
resulting solutionwas light amber in color. The presence of some particulate
indicated that the polymer was not fully dissolved. Final solids content was
11.0%.
ative Example G
The materials and procedures of Example 6 were reproduced except that
the NMMO/HZO ratio was adjusted to a different value as shown in Table 2. The
ing solutionwas light amber in color. The presence of some particulate
indicated that the polymer was not fully dissolved. Final solids content was
.8%.
Comparative Example H
The materials and procedures of Example 6 were reproduced except that
the NMMO/HZO ratio was adjusted to a different value as shown in Table 2. In
addition, following the vacuum distillation of water, the vacuum was turned off,
the mixture was blanketed with nitrogen, and allowed to continue heating at 110
°C for an additional 60 minutes with occasional . The resulting solution
was light amber in color. The presence of some ulate indicated that the
polymer was not fully dissolved. Final solids content was 10.8%.
Example 7
0.5g of polymer P3 was suspended in a mixture containing 6g of NMMO
and 6 ml of an aqueous solution of propyl gallate (0.08M) and ylamine
sulfate (0.026 M) . The ingredients were charged into a 40 ml glass vial fitted
with a silicone septum and stirring rod. After charging the vial and its ts
were capped and weighed. The mixture was then heated at 110 0C for 30
minutes with occasional manual . After 30 minutes vacuum was applied
while heating at 110 CC to remove water to the level shown in the table. following
the vacuum tion of water, the vacuum was turned off, the mixture was
blanketed with nitrogen, and allowed to continue heating at 110 CC for an
onal 3 hours with occasional mixing. The resulting solution was completely
clear and was light amber in color. Final solids content was 5.6%
Example 8
0.5g of polymer P3 was suspended in a mixture containing 5g NMMO and
ml of an aqueous solution of propyl gallate (0.08M) and hydroxylamine sulfate
(0.026 M) . The equipment and procedures of Example 7 were repeated. The
resulting solution was completely clear and was light amber in color. Final solids
content was 6.3%
0.5 g of polymer P3 was suspended in a mixture 4g NMMO and 4
ml of an aqueous solution of propyl gallate (0.08M) and ylamine sulfate
(0.026 M) . The equipment and procedures of e 7 were ed. The
resulting solution was completely clear and was light amber in color. Final solids
content was 8.7%
Comparative Example I
0.5 g of polymer P3 was suspended in a mixture ning 3g NMMO and
3 ml of an aqueous solution of propyl gallate (0.08M) and hydroxylamine sulfate
(0.026 M) . The equipment and procedures of Example 7 were repeated. After 3
hours the glucan polymer was gel like with some particulate and was light amber
in color. Final solids content was 10.1%
Example 10
3.17 g of 97 % NMMO was transferred to a tared 20 x 125 mm tissue
culture tube. 1.63 g (excess) de-ionized water was added to the tube. The tube
was capped with a septum, and a plastic stirring rod was inserted through a pre-
bored Teflon®-coated silicone septum. The mixture so formed was stirred for
approximately 1 minute. After stirring, 0.12 ml of a stabilized aqueous solution
ning 0.4 wt % hydroxylamine sulfate and 1.7 wt % propyl gallate was
added to the tube and further mixing was conducted for 2 to 5 minutes. 0.25 g of
r P5 was added to the tube and the resulting mixture was mixed at room
temperature for an additional 2 to 5 minutes, forming a slurry.
Behind a glass shield, the tube was placed in a Pierce Reacti-therm
heating module (Pierce hnology, Rockford,lL) at 50 °C. The contents of
the tube were blanketed with nitrogen ed through a needle inserted
through the . The tube was thus heated in the block at 50 °C for 30 to 45
minutes, stirring intermittently by hand every 5 to 10 minutes. The polymer solids
were observed to have been thoroughly wetted. The temperature was then
raised to 100 °C over a period of 15 minutes and then held at 100 0C for 30 to 60
minutes to begin dissolution while mixing intermittently. Maintaining stirring, the
temperature was then increased to 115 oC and excess water was removed under
, stirring intermittently, to the concentration shown in Table 2, and to
complete formation of the solution. The final composition was as shown in Table
2. The polymer was completely dissolved. Solids content of 6.84wt% was
verified by weight loss of water and confirmation by GC-MS that the distillate
contained a negligible amount of NMMO.
Examples 11 — 17 and Comparative Examples J - P
The als and procedures employed in e 10 were repeated
with the changes indicated in Table 2. Results are shown in Table 2.
2012/058850
Table 2
NMMO H20 NMMO/
Amount Solids Solution
Example Designation DP Content Content water
(9) (%) Forming?
(final, 9) (final,g) (wt/wt)
Ex. 4 P2 0.5 870 4 1.13 3.54 8.88 yes
Ex. 5 P4 1 255 8.5 2.84 2.99 8.1 yes
Ex. 6 P1 8 403 46 19.3 2.38 10.91 yes
Comp. Ex.E P1 10 403 46 16.9 2.72 13.72 no
Comp. Ex.F P1 8 403 46 18.6 2.47 11.02 no
Comp. Ex.G P1 8 403 46 20.25 2.27 10.77 no
Comp. Ex.H P1 8 403 46 20.4 2.25 10.75 no
Ex. 7 P4 0.5 255 6 2.48 2.42 5.57 yes
Ex. 8 P4 0.5 255 5 2.48 2.02 6.27 yes
Ex. 9 P4 0.5 255 4 1.28 3.13 8.65 yes
Comp. Ex. I P4 0.5 255 3 1.47 2.04 10.06 no
Ex. 10 P5 0.25 372 3.17 0.38 8.34 6.84 yes
Ex. 11 P5 0.3 372 3.18 0.37 8.59 8.06 yes
Ex. 12 P5 0.54 372 3.18 0.35 9.09 14.82 yes
Ex. 13 P5 0.3 372 4.52 1.26 3.59 5.15 yes
Ex. 14 P5 0.36 372 3.04 0.29 10.48 10.15 yes
Ex. 15 P5 0.42 372 3.06 0.37 8.27 11.92 yes
Ex. 16 P5 0.35 372 3.05 0.26 11.73 9.89 yes
Ex. 17 P5 0.43 372 3.1 0.35 8.86 12.07 yes
Comp. Ex. J P6 0.68 110 3.4 1.7 2 17.21 no
Comp. Ex. K P5 0.69 372 3.09 0.55 5.62 19.37 no
Comp. Ex. L P5 0.88 372 3.02 0.48 6.29 25.26 no
Comp. Ex.
P5 0.23 372 2.26 2.26 1 4.91 no
Comp. Ex. N P5 0.47 372 2.27 2.27 1 10.08 no
Comp. Ex. 0 P5 0.7 372 2.27 2.27 1 15.18 no
Comp. Ex. P P5 0.93 372 2.28 2.28 1 19.92 no
Claims (14)
1. A solution comprising N-methylmorpholine-N-oxide (NMMO), water, and poly(α(13) glucan) wherein the concentration of poly(α(13) glucan) is in 5 the range of 5 – 20 % by weight with t to the total weight of the solution, wherein the lpha(13) glucan) has at least 50% of the linkages between glucose repeat units as α(13) glycoside linkages and a number average molecular weight (Mn) of at least 10,000 Da; and, wherein the weight ratio of NMMO to water is in the range of 12 to 1.6.
2. The solution of Claim 1, in the form of an isotropic solution.
3. The solution of Claim 1, wherein, in the poly(α(13) glucan), at least 90 mol-% of the repeat units in the r are glucose repeat units.
4. The solution of Claim 3, wherein, in the poly(α(13) glucan) 100 mol-% of the repeat units in the polymer are glucose repeat units and at least 100 % of the linkages between glucose repeat units are α(13) glycoside
5. The solution of Claim 1, wherein the concentration of poly(α(13) glucan) is in the range of 10 to 15 % by weight.
6. The solution of Claim 1, wherein the number average molecular weight of 25 the poly(alpha(13) glucan) is in the range of 50,000 to 70,000 Daltons.
7. A process for ing a poly(alpha(13) glucan) fiber, comprising the steps of: dissolving in a mixture of N-methylmorpholine-N-oxide (NMMO) and water, 5 to 20 % by weight of the total weight of the resulting solution of 30 poly(alpha(13) glucan) wherein the poly(alpha(13) ) has a number average molecular weight (Mn) of at least 10,000 Da, to form a solution, wherein the weight ratio of NMMO to water in said solution is in the range of 12 to 1.6; g said solution to flow through a spinneret, forming a fiber thereby, using a liquid ant to t the NMMO from the thus formed fiber.
8. The process of Claim 7, wherein the solution is in the form of an pic 5 solution.
9. The process of Claim 7, wherein at least 90 mol-% of the repeat units in the poly(alpha(1 3) glucan) are glucose repeat units.
10 10. The process of Claim 9, wherein 100 mol-% of the repeat units, in the poly( α(1 3) glucan) are glucose repeat units and at least 100 % of the linkages between glucose repeat units are α(1 3) glycoside linkages.
11. The process of Claim 7, wherein the tration of poly(α(1 3) glucan) 15 in the solution is in the range of 10 to 15 % by weight.
12. The process of Claim 7, wherein the number average molecular weight of the poly(alpha(1 3) glucan) in the solution is in the range of 50,000 to 70,000 Daltons.
13. The process of Claim 7, wherein the liquid coagulant is glacial acetic acid.
14. The process of Claim 7, wherein the liquid coagulant is a mixture of N- methylmorpholine N oxide and water having a water concentration of at 25 least 75 % by weight.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161543423P | 2011-10-05 | 2011-10-05 | |
US61/543,423 | 2011-10-05 | ||
PCT/US2012/058850 WO2013052730A1 (en) | 2011-10-05 | 2012-10-05 | Novel composition for preparing polysaccharide fibers |
Publications (2)
Publication Number | Publication Date |
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NZ623330A NZ623330A (en) | 2016-02-26 |
NZ623330B2 true NZ623330B2 (en) | 2016-05-27 |
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