WO2015144983A1 - Starch nanoparticles and process for the manufacture thereof - Google Patents
Starch nanoparticles and process for the manufacture thereof Download PDFInfo
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- WO2015144983A1 WO2015144983A1 PCT/FI2015/050181 FI2015050181W WO2015144983A1 WO 2015144983 A1 WO2015144983 A1 WO 2015144983A1 FI 2015050181 W FI2015050181 W FI 2015050181W WO 2015144983 A1 WO2015144983 A1 WO 2015144983A1
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- Prior art keywords
- starch
- nanoparticles
- process according
- starches
- slurry
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Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 208
- 235000019698 starch Nutrition 0.000 title claims abstract description 203
- 239000008107 starch Substances 0.000 title claims abstract description 183
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 56
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 238000000265 homogenisation Methods 0.000 claims abstract description 19
- 239000012736 aqueous medium Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 24
- 229920000881 Modified starch Polymers 0.000 claims description 15
- 235000019426 modified starch Nutrition 0.000 claims description 15
- 229920001592 potato starch Polymers 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 240000003183 Manihot esculenta Species 0.000 claims description 9
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 9
- 239000004368 Modified starch Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010408 film Substances 0.000 claims description 8
- 229920002261 Corn starch Polymers 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 244000205754 Colocasia esculenta Species 0.000 claims description 6
- 235000006481 Colocasia esculenta Nutrition 0.000 claims description 6
- 240000005979 Hordeum vulgare Species 0.000 claims description 6
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 6
- 244000062793 Sorghum vulgare Species 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000008120 corn starch Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229940100486 rice starch Drugs 0.000 claims description 5
- 229940100445 wheat starch Drugs 0.000 claims description 5
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 4
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 4
- 240000004713 Pisum sativum Species 0.000 claims description 4
- 235000010582 Pisum sativum Nutrition 0.000 claims description 4
- 244000061456 Solanum tuberosum Species 0.000 claims description 4
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000002537 cosmetic Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 239000000834 fixative Substances 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 239000008194 pharmaceutical composition Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 241000082175 Arracacia xanthorrhiza Species 0.000 claims description 3
- 235000007319 Avena orientalis Nutrition 0.000 claims description 3
- 244000075850 Avena orientalis Species 0.000 claims description 3
- 235000005273 Canna coccinea Nutrition 0.000 claims description 3
- 240000008555 Canna flaccida Species 0.000 claims description 3
- 244000045195 Cicer arietinum Species 0.000 claims description 3
- 235000010523 Cicer arietinum Nutrition 0.000 claims description 3
- 240000000745 Erythronium japonicum Species 0.000 claims description 3
- 235000000495 Erythronium japonicum Nutrition 0.000 claims description 3
- 240000008620 Fagopyrum esculentum Species 0.000 claims description 3
- 235000009419 Fagopyrum esculentum Nutrition 0.000 claims description 3
- 235000010804 Maranta arundinacea Nutrition 0.000 claims description 3
- 240000005561 Musa balbisiana Species 0.000 claims description 3
- 235000008469 Oxalis tuberosa Nutrition 0.000 claims description 3
- 244000079423 Oxalis tuberosa Species 0.000 claims description 3
- 235000010575 Pueraria lobata Nutrition 0.000 claims description 3
- 244000046146 Pueraria lobata Species 0.000 claims description 3
- 235000007238 Secale cereale Nutrition 0.000 claims description 3
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 3
- 235000003206 Tacca pinnatifida Nutrition 0.000 claims description 3
- 244000145580 Thalia geniculata Species 0.000 claims description 3
- 235000012419 Thalia geniculata Nutrition 0.000 claims description 3
- 229920008262 Thermoplastic starch Polymers 0.000 claims description 3
- 240000004922 Vigna radiata Species 0.000 claims description 3
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 3
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- 238000005538 encapsulation Methods 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 235000019713 millet Nutrition 0.000 claims description 3
- 235000012015 potatoes Nutrition 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000006254 rheological additive Substances 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 2
- 235000019759 Maize starch Nutrition 0.000 claims 2
- 244000003502 Tacca pinnatifida Species 0.000 claims 2
- 229920006320 anionic starch Polymers 0.000 claims 2
- 235000009508 confectionery Nutrition 0.000 claims 2
- 238000009826 distribution Methods 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000945 Amylopectin Polymers 0.000 description 5
- 229920000856 Amylose Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
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- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
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- 244000098338 Triticum aestivum Species 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 235000013804 distarch phosphate Nutrition 0.000 description 2
- 239000001245 distarch phosphate Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 235000009566 rice Nutrition 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000807 solvent casting Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- 239000004370 Bleached starch Substances 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004362 Hydroxy propyl distarch glycerol Substances 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- 229920003012 Hydroxypropyl distarch phosphate Polymers 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 229920002985 Phosphated distarch phosphate Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- MKRNVBXERAPZOP-UHFFFAOYSA-N Starch acetate Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OC(C)=O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 MKRNVBXERAPZOP-UHFFFAOYSA-N 0.000 description 1
- 240000002033 Tacca leontopetaloides Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000013770 acetylated oxidized starch Nutrition 0.000 description 1
- 239000001073 acetylated oxidized starch Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 235000019428 bleached starch Nutrition 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000001487 glyoxylate group Chemical class O=C([O-])C(=O)[*] 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 235000019434 hydroxy propyl distarch glycerol Nutrition 0.000 description 1
- 235000013825 hydroxy propyl distarch phosphate Nutrition 0.000 description 1
- 239000001310 hydroxy propyl distarch phosphate Substances 0.000 description 1
- DVROLKBAWTYHHD-UHFFFAOYSA-N hydroxy propyl distarch phosphate Chemical compound OC1C(O)C(OC)OC(CO)C1OC(O)CCOC1C(OC2C(C(O)C(OC3C(C(OP(O)(=O)OC4C(C(O)C(OC)OC4CO)O)C(C)OC3CO)O)OC2COC2C(C(O)C(OC)C(CO)O2)O)O)OC(CO)C(OC)C1O DVROLKBAWTYHHD-UHFFFAOYSA-N 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 235000015250 liver sausages Nutrition 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 235000013807 monostarch phosphate Nutrition 0.000 description 1
- 239000001248 monostarch phosphate Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 235000013803 phosphated distarch phosphate Nutrition 0.000 description 1
- 239000001239 phosphated distarch phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000013826 starch sodium octenyl succinate Nutrition 0.000 description 1
- 239000001334 starch sodium octenyl succinate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/06—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/08—Ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
- C08J2303/06—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
- C08J2303/08—Ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
Definitions
- the invention relates to a new process for the manufacture of starch nanoparticles and nanostarch. Further, the invention relates to starch nanoparticles and nanostarch obtainable by the process, as well as uses of said starch nanoparticles and nanostarch.
- Starches are naturally occurring biodegradable polymers obtainable from renewable resources. Starches are traditionally used in several areas of industry, in applications such as pigments, barrier dispersions, flocculants, fixatives, films, additives in paper manufacture, adhesives, coatings, rheology stabilizers, pharmaceutical formulations, cosmetics, food etc. The amount of starch required for the above mentioned applications is typically high. The commercially most important sources of starch are corn, wheat, rice, potatoes, tapioca and peas.
- starch is a linear polymer consisting of p-l,4-linked D- glucose.
- Starch may contain pure amylopectin or it may be a mixture of amylose (typically 20-30%) and amylopectin (typically 70-80%).
- Amylose is a linear polysaccharide consisting of a-l,4-linked D-glucose.
- Amylopectin is an extremely high molecular weight polymer having the same backbone structure as amylose but with many a-l,6-linked branch points.
- Native starch occurs in the form of discrete, partially crystalline microscopic granules that are held together by an extended micellar network of associated molecules.
- Liu D et al Journal of Colloid and Interphase Science 339 (2009) 117-124, describes a method for reducing particle size of high amylose corn starch to nano-size by subjecting a 5 w-% aqueous slurry of said corn starch to high-pressure homogenization, followed by cooling on ice bath and repeating the homogenization.
- the inventors of the present application were not able to repeat the method of Liu et al. for producing nano-sized starch.
- An object of the present invention is to provide a new process for the manufacture of starch nanoparticles.
- a further object is to provide starch nanoparticles obtainable by the method.
- a still further object is to provide uses of said starch nanoparticles.
- aspects of the invention are thus directed to a process for the manufacture of starch nanoparticles, said process comprising the steps of providing an aqueous dispersion comprising starch, homogenizing the dispersion in a homogenizer at a temperature between 30 and 80°C to yield a gelatinized slurry, diluting the gelatinized slurry with an aqueous medium to obtain starch content between 0.01 and 10 wt%, and homogenizing the diluted gelatinized slurry in a homogenizer at the temperature of 3- 20°C for 1 to 30 passes to obtain starch nanoparticles.
- aspects of the invention are also directed to a nanostarch and starch nanoparticles.
- Said starch nanoparticles are obtainable by the process described above.
- aspects of the invention are also directed to the use and method of use of the starch nanoparticles in applications, such as in barrier dispersions, pigments, films, flocculants, rheology modifiers, glues, adhesives, dispersion agents, thermoplastics, composites, water purification applications, cosmetics, pharmaceutical formulations, encapsulation agents, retention aids, sizing agents, fixatives, cleaning agents, and detergents, etc.
- Figure 1 shows particle size distributions of native potato starch (Fig. la), and starch nanoparticles obtained in example 1 (Fig. lb).
- Figure 2 illustrates SEM images of the starch nanoparticles obtained in Example 1, in
- Figure 3 shows the viscosity of the homogenized slurry as function of shear rate of starch nanoparticles manufactured from potato starch using the process of the invention after 2, and 6, 12, 15 and 18 passes, as manufactured in example 2.
- starch nanoparticles or “nanostarch” refers here to nanoparticles of starch, having average particle size below 1 ⁇ .
- starch nanoparticles can be manufactured in a simple and efficient way, utilizing the process of the invention.
- an aqueous medium is added to the gelatinized slurry in a volumetric ratio of 1 : 1 or more to obtain diluted gelatinized slurry.
- Said diluted gelatinized slurry has starch content of 0.01-10 wt%, preferably 0.1-7 wt% and particularly preferably 0.1-6 wt%.
- the diluted gelatinized slurry is subjected to homogenization, which is carried out for 1-30 passes (times), preferably for 2-18 passes and particularly preferably for 2-9 passes.
- the diluted gelatinized slurry is subjected to homogenization at the temperature of 3-20°C, preferably 8-18°C, particularly preferably 10-15°C.
- the slurry is directed through a heat exchanger, which removes heat during the processing and keeps the diluted slurry at the temperature of 3-20°C, preferably 8-18°C, particularly preferably 10- 15°C.
- Nanostarch slurry comprising starch nanoparticles is obtained.
- 0.1 - 20 % by weight preferably 0.5 - 15 % by weight, particularly preferably 2 - 10 % by weight of starch is dispersed in an aqueous medium to obtain an aqueous dispersion.
- the starch is selected from native and modified starches, and any combinations thereof. Suitably starches with high amylopectin content and which starches can be gelatinized, are used.
- the major sources of native starch are the cereals, the root vegetables and many kinds of beans.
- Examples of such starches are rice, wheat, barley, maize, potato and cassava, and favas, lentila, mung beans, peas, and chickpeas starches.
- starchy plants which are grown, some only in specific climates, and thus acors, arrowroot, arracacha, bananas, beadfruit, buckwheat, canna, colacasia, katakuri kudzu, malanga, millet, oats, oca, Polynesian arrowroot, sago, sorghum, sweet potatoes, rye, taro, chesnut, water chesnut, yams starches may also be used.
- the native starch is selected from potato starch, corn starch, barley starch, wheat starch, tapioca starch, bean starch, rice starch, particularly preferably potato starch is used.
- Modified starch is starch that has been chemically modified. Examples of modified starches are presented as follows: Dextrin, acid-treated starch, alkaline-treated starch, bleached starch, oxidized starch, enzyme-treated starch, monostarch phosphate, distarch phosphate, phosphated distarch phosphate, acetylated distarch phosphate, starch esters, starch ethers, acetylated distarch ad i pate, hydroxypropyl starch, hydroxypropyl distarch phosphate, hydroxypropyl distarch glycerol, starch sodium octenyl succinate, and acetylated oxidized starch.
- the modified starch is selected from cationic (cationized) starches having DS (degree of substitution) of not more than 0.2, anionized starches having DS of not more than 0.3, thermoplastic starches, starch ethers and starch esters.
- cationized potato starch is used.
- the aqueous medium is dispersed with starch suitably at the temperature of 1-50°C, preferably at a temperature of 4-30°C to obtain an aqueous dispersion.
- the obtained nanostarch slurry may be subjected to drying.
- Said drying may be carried out as spray-drying, drying under vacuum, with heat, or as freeze-drying (lyophilization).
- the starch nanoparticles obtained from native grade starches are freeze-dried or dried under vacuum at temperatures below 40°C.
- the starch nanoparticles obtained from modified grades of starches may also be dried at elevated temperatures, suitable at temperatures not more than 80°C. Typically finely divided nanostarch powder is obtained.
- the process of the invention can be up-scaled to larger industrial scale without problems.
- the obtained starch nanoparticles have average particle size of less than 1 ⁇ , preferably not more than 200 nm, particularly preferably 20-100 nm.
- the average particle size and particle size distribution of starch nanoparticles may be measured using any apparatus for measuring particle size, such as Coulter counter, methods based on laser diffraction, TEM (transmission electron microscopy), SEM (scanning electron microscopy, back-scattered quasi-elastic light scattering device etc.
- the dry starch nanoparticles are typically in the form of a free flowing powder.
- the obtained starch nanoparticles have improved properties when compared with traditional starches.
- Particularly the obtained starch nanoparticles have improved reaction efficiency and reactivity in further chemical modifications. This results in that less chemicals are needed for the modifications due to the increased amount of active surface. No visible aggregation takes place during drying of the obtained starch nanoparticles. Further, they have improved film-forming ability and clear, transparent and homogenous films with even surface are obtained. Thin films may be obtained with for example solvent casting methods from unmodified and modified nanostarches.
- the viscosity of aqueous dispersions formed of said nanostarch particles is decreased when compared to the ones obtained with native starch.
- the performance of the obtained starch nanoparticles is improved when compared with native starch. The costs are reduced in various applications, because lower amounts of other chemicals are needed due to the increased active surface area provided by the starch nanoparticles, and thus the loading of the particles can be altogether decreased.
- the excellent film-forming is a significant advantage, as well as drying of the starch nanoparticles without aggregation or other problems. Further, the ease of manufacture of the starch nanoparticles, applicability of the starch nanoparticles to various uses, possibility to design the properties of starch nanoparticles according to the intended use are some examples of the desired benefits achieved by the present invention.
- the slurry was in the first step fluidized under high shear, under a pressure of 1850 bar or 2050 bar and at the temperature above 30°C to effect gelatinization whereby gelatinized slurry was obtained.
- a heat exchanger was used for controlling the temperature of the output slurry in the range of 10-15°C.
- Said slurry was diluted with RO water to a consistency of 5 wt%, calculated based on dry matter.
- said diluted gelatinized slurry was subjected to homogenization (in the same apparatus as in the first step) under a pressure of 1850 bar or 2050 bar and at the temperature of 10-15°C, where practically no gelatinization took place. Under the constant pressure the slurry passed through the interaction chambers and nano- sized material was obtained.
- Potato starch was dispersed in an aqueous mixture of ion-exchanged water containing 1 % by volume of ethanol to obtain a 10 wt% aqueous dispersion, calculated by dry substance.
- the dispersion was mixed in a blender to obtain homogenous slurry. No pH adjustment was needed.
- the slurry was poured in to a microfluidizer M l lOEH for effecting high-pressure homogenization.
- the slurry was in the first step fluidized for two passes under high shear, under a pressure of 1850 bar or 2050 bar and at the temperature above 30°C to effect gelatinization whereby gelatinized slurry was obtained.
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Abstract
The invention relates to a starch nanoparticles and a process for the manufacture of said starch nanoparticles, comprising the steps, where in the first step starch is dispersed in an aqueous medium to obtain an aqueous dispersion, which is subjected to homogenization at a temperature between 30 and 80°C to yield a gelatinized slurry, in the second step aqueous medium is added to the gelatinized slurry in a volumetric ratio of 1:1 or more to obtain diluted gelatinized slurry and homogenizing the diluted gelatinized slurry at the temperature of 3-20°C for 1 to 30 passes to obtain starch nanoparticles. The invention also relates to uses of starch nanoparticles.
Description
STARCH NANOPARTICLES AND PROCESS FOR THE MANUFACTURE THEREOF
FIELD OF THE INVENTION
The invention relates to a new process for the manufacture of starch nanoparticles and nanostarch. Further, the invention relates to starch nanoparticles and nanostarch obtainable by the process, as well as uses of said starch nanoparticles and nanostarch.
BACKGROUND
Starches are naturally occurring biodegradable polymers obtainable from renewable resources. Starches are traditionally used in several areas of industry, in applications such as pigments, barrier dispersions, flocculants, fixatives, films, additives in paper manufacture, adhesives, coatings, rheology stabilizers, pharmaceutical formulations, cosmetics, food etc. The amount of starch required for the above mentioned applications is typically high. The commercially most important sources of starch are corn, wheat, rice, potatoes, tapioca and peas.
By the chemical structure starch is a linear polymer consisting of p-l,4-linked D- glucose. Starch may contain pure amylopectin or it may be a mixture of amylose (typically 20-30%) and amylopectin (typically 70-80%). Amylose is a linear polysaccharide consisting of a-l,4-linked D-glucose. Amylopectin is an extremely high molecular weight polymer having the same backbone structure as amylose but with many a-l,6-linked branch points. Native starch occurs in the form of discrete, partially crystalline microscopic granules that are held together by an extended micellar network of associated molecules. The semi-crystalline structure of starch is attributed to the short-chain fraction of amylopectin, arranged as double helices and packed in crystallites. Typically the average particle size of native starch and modified starch is in the range of 1-40 μιη. Starch typically aggregates readily when drying, and it has limited film-forming ability, if any and high viscosity in aqueous solutions. These properties limit the use of native starches and require further chemicals in formulations whereby costs are increased .
Starch nanoparticles have recently received interest because of their biocompatibility, biodegradability and nontoxicity in several fields of industry, particularly in nanotechnology, and in food and pharmaceutical applications.
Liu D et al, Journal of Colloid and Interphase Science 339 (2009) 117-124, describes a method for reducing particle size of high amylose corn starch to nano-size by subjecting a 5 w-% aqueous slurry of said corn starch to high-pressure homogenization, followed by cooling on ice bath and repeating the homogenization. The inventors of the present application were not able to repeat the method of Liu et al. for producing nano-sized starch.
Thus there is a need for a simple and reliable method, which is workable also on an industrial scale, for producing starch nanoparticles.
SUM MARY
An object of the present invention is to provide a new process for the manufacture of starch nanoparticles.
A further object is to provide starch nanoparticles obtainable by the method. A still further object is to provide uses of said starch nanoparticles.
Aspects of the invention are thus directed to a process for the manufacture of starch nanoparticles, said process comprising the steps of providing an aqueous dispersion comprising starch, homogenizing the dispersion in a homogenizer at a temperature between 30 and 80°C to yield a gelatinized slurry, diluting the gelatinized slurry with an aqueous medium to obtain starch content between 0.01 and 10 wt%, and homogenizing the diluted gelatinized slurry in a homogenizer at the temperature of 3- 20°C for 1 to 30 passes to obtain starch nanoparticles.
Aspects of the invention are also directed to a nanostarch and starch nanoparticles. Said starch nanoparticles are obtainable by the process described above.
Aspects of the invention are also directed to the use and method of use of the starch nanoparticles in applications, such as in barrier dispersions, pigments, films, flocculants, rheology modifiers, glues, adhesives, dispersion agents, thermoplastics, composites, water purification applications, cosmetics, pharmaceutical formulations,
encapsulation agents, retention aids, sizing agents, fixatives, cleaning agents, and detergents, etc.
Particularly, the ease of manufacture of the starch nanoparticles, applicability of the starch nanoparticles to various uses, possibility to design the properties of starch nanoparticles according to the intended use are some examples of the desired benefits achieved by the present invention.
The characteristic features of the invention are presented in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows particle size distributions of native potato starch (Fig. la), and starch nanoparticles obtained in example 1 (Fig. lb). Figure 2 illustrates SEM images of the starch nanoparticles obtained in Example 1, in
Fig. 2a 2 passes and in Fig. 2b 12 passes.
Figure 3 shows the viscosity of the homogenized slurry as function of shear rate of starch nanoparticles manufactured from potato starch using the process of the invention after 2, and 6, 12, 15 and 18 passes, as manufactured in example 2.
DEFINITIONS
Unless otherwise specified, the terms, which are used in the specification and claims, have the meanings commonly used in the field of starch chemistry and processing, as well as in the various application fields of starch. Specifically, the following terms have the meanings indicated below.
The term "starch nanoparticles" or "nanostarch" refers here to nanoparticles of starch, having average particle size below 1 μιη.
The term "homogenization" refers here to disintegration or fluidization under high pressure and high shear. Any high-pressure and high-shear homogenizers, fluidizers, micro-fluidizers, and disintegrators can be used.
The term "passes" refer to how many times the slurry etc is run in/through the homogenizer.
DETAILED DESCRIPTION OF THE INVENTION
It was surprisingly found that starch nanoparticles can be manufactured in a simple and efficient way, utilizing the process of the invention.
Process
The process according to the invention comprises the steps of providing an aqueous dispersion comprising starch, homogenizing said dispersion in a homogenizer at a temperature between 30 and 80°C to yield a gelatinized slurry, diluting the gelatinized slurry with an aqueous medium to obtain starch content between 0.01 and 10 wt%, and homogenizing the diluted gelatinized slurry in a homogenizer at the temperature of 3-20°C for 1 to 30 passes to obtain starch nanoparticles.
Particularly the process for the manufacture of starch nanoparticles comprises the steps, where in the first step starch is dispersed in an aqueous medium to obtain an aqueous dispersion, which is subjected to homogenization, suitably for 1-3 passes, preferably one pass, at the temperature of 30-80°C, preferably 40-75°C, particularly preferably 50-75°C to effect gelatinization whereby a gelatinized slurry is obtained. Optionally the gelatinized slurry may further be homogenized, suitably for 1-2 passes, at the temperature of 3-20°C, preferably 8-18°C.
In the second step an aqueous medium is added to the gelatinized slurry in a volumetric ratio of 1 : 1 or more to obtain diluted gelatinized slurry. Said diluted gelatinized slurry has starch content of 0.01-10 wt%, preferably 0.1-7 wt% and particularly preferably 0.1-6 wt%. The diluted gelatinized slurry is subjected to homogenization, which is carried out for 1-30 passes (times), preferably for 2-18 passes and particularly preferably for 2-9 passes. The diluted gelatinized slurry is subjected to homogenization at the temperature of 3-20°C, preferably 8-18°C, particularly preferably 10-15°C. Suitably after each pass the slurry is directed through a heat exchanger, which removes heat during the processing and keeps the diluted slurry at the temperature of 3-20°C, preferably 8-18°C, particularly preferably 10- 15°C. Nanostarch slurry comprising starch nanoparticles is obtained.
In the first step 0.1 - 20 % by weight, preferably 0.5 - 15 % by weight, particularly preferably 2 - 10 % by weight of starch is dispersed in an aqueous medium to obtain an aqueous dispersion.
The starch is selected from native and modified starches, and any combinations thereof. Suitably starches with high amylopectin content and which starches can be gelatinized, are used.
The major sources of native starch are the cereals, the root vegetables and many kinds of beans. Examples of such starches are rice, wheat, barley, maize, potato and cassava, and favas, lentila, mung beans, peas, and chickpeas starches. However, there are many other starchy plants, which are grown, some only in specific climates, and thus acors, arrowroot, arracacha, bananas, beadfruit, buckwheat, canna, colacasia, katakuri kudzu, malanga, millet, oats, oca, Polynesian arrowroot, sago, sorghum, sweet potatoes, rye, taro, chesnut, water chesnut, yams starches may also be used. Preferably the native starch is selected from potato starch, corn starch, barley starch, wheat starch, tapioca starch, bean starch, rice starch, particularly preferably potato starch is used.
Modified starch is starch that has been chemically modified. Examples of modified starches are presented as follows: Dextrin, acid-treated starch, alkaline-treated starch, bleached starch, oxidized starch, enzyme-treated starch, monostarch phosphate, distarch phosphate, phosphated distarch phosphate, acetylated distarch phosphate, starch esters, starch ethers, acetylated distarch ad i pate, hydroxypropyl starch, hydroxypropyl distarch phosphate, hydroxypropyl distarch glycerol, starch sodium octenyl succinate, and acetylated oxidized starch. Typical modified starches for technical applications and useful in the presesnt invention are cationic (positively charged) starches, hydroxyethyl starches, carboxymethylated starches and starch acetate, starch propionate, starch butyrate, starch hexanoate and other starch esters.
Preferably the modified starch is selected from cationic (cationized) starches having DS (degree of substitution) of not more than 0.2, anionized starches having DS of not more than 0.3, thermoplastic starches, starch ethers and starch esters. Suitably cationized potato starch is used.
Water soluble charged starches may also be used, however they require, prior to the dispersing step, cross-linking with a suitable cross-linking agent, such as borax (boric acid), saccharin, citric acid, glyoxylates and the like whereby the water solubility is decreased, and the product can be ground.
The aqueous medium is selected from water and mixtures of water with a C1-C4 alcohol or acetone or methyl ethyl ketone or with combinations thereof. A preferable alcohol is ethanol. Water used in the process may be tap water or purified water,
preferably purified water selected from RO (reverse osmosis) water, deionized water, distilled water and water purified with other means is used. The content of alcohol or ketone in said aqueous medium is suitably not more than 5 % by volume, preferably 0.1-2 % by volume. Alcohols and ketones reduce air bubble formation during homogenizing. The aqueous medium used in the first step may be the same or different from the one used in the second step. Preferably the same aqueous medium is used in both steps.
In the first step the aqueous medium is dispersed with starch suitably at the temperature of 1-50°C, preferably at a temperature of 4-30°C to obtain an aqueous dispersion.
If necessary, the pH of the dispersion is adjusted to 4-8, preferably to 6-7.5 with an acid or base, such as HCI, citric acid, sodium hydroxide etc. Typically there is no need for pH adjustment when native starches are used, but when modified starches are used the pH adjustment may be necessary.
The homogenization (fluidizing, disintegration) is carried out under the pressure of 100-2200 bar, in the first and subsequent homogenization steps. The homogenization may be carried out using any high-shear homogenizers, fluidizers, microfluidizers, or ultrasonic homogenizers etc.
After the homogenization steps are completed the obtained nanostarch slurry may be subjected to drying. Said drying may be carried out as spray-drying, drying under vacuum, with heat, or as freeze-drying (lyophilization). Suitably the starch nanoparticles obtained from native grade starches are freeze-dried or dried under vacuum at temperatures below 40°C. The starch nanoparticles obtained from modified grades of starches may also be dried at elevated temperatures, suitable at temperatures not more than 80°C. Typically finely divided nanostarch powder is obtained.
The process of the invention can be up-scaled to larger industrial scale without problems.
Product
The obtained starch nanoparticles have average particle size of less than 1 μιη, preferably not more than 200 nm, particularly preferably 20-100 nm.
The average particle size and particle size distribution of starch nanoparticles may be measured using any apparatus for measuring particle size, such as Coulter counter, methods based on laser diffraction, TEM (transmission electron microscopy), SEM (scanning electron microscopy, back-scattered quasi-elastic light scattering device etc.
The dry starch nanoparticles are typically in the form of a free flowing powder.
The starch nanoparticles have specific surface are of 10-70 m2/g, preferably 10-60 m2/g- The determination of the specific surface area is based on laser diffraction using samples in wet state. In the laser diffraction method the particle size distributions of the dispersions are characterized by laser diffraction (such as Coulter LS230, Beckman Coulter, CA) using refractive indices 1.53 and 1.333 for particles and media (water), respectively. At least two replicate samples are analysed in two consecutive measurements, of which the average geometric volume distributions, the standard deviation for mean value and the specific surface area are calculated.
The viscosity of aqueous dispersions of said nanostarch particles is typically 1-100 mPa*s, preferably 2-80 mPa*s, and particularly preferably 2-50 mPa*s, even more preferably 2-10 mPa*s, measured using a cone and plate rheometer in shear rate range of 0.2-500 1/s, using 5 wt% sample content and the temperature of 21°C.
The obtained starch nanoparticles have improved properties when compared with traditional starches. Particularly the obtained starch nanoparticles have improved reaction efficiency and reactivity in further chemical modifications. This results in that less chemicals are needed for the modifications due to the increased amount of active surface. No visible aggregation takes place during drying of the obtained starch nanoparticles. Further, they have improved film-forming ability and clear, transparent and homogenous films with even surface are obtained. Thin films may be obtained with for example solvent casting methods from unmodified and modified nanostarches. The viscosity of aqueous dispersions formed of said nanostarch particles is decreased when compared to the ones obtained with native starch. The performance of the obtained starch nanoparticles is improved when compared with native starch. The costs are reduced in various applications, because lower amounts of other chemicals are needed due to the increased active surface area provided by the starch nanoparticles, and thus the loading of the particles can be altogether decreased.
Particularly the excellent film-forming is a significant advantage, as well as drying of the starch nanoparticles without aggregation or other problems. Further, the ease of
manufacture of the starch nanoparticles, applicability of the starch nanoparticles to various uses, possibility to design the properties of starch nanoparticles according to the intended use are some examples of the desired benefits achieved by the present invention. The obtained nanostarch and starch nanoparticles can be used for example in applications where starch is traditionally used, such as in barrier dispersions, pigments, films, flocculants, rheology modifiers, glues, adhesives, dispersion agents, thermoplastics, composites, water purification applications, cosmetics, pharmaceutical formulations, encapsulation agents, retention aids, sizing agents, fixatives, cleaning agents, and detergents.
The following examples are illustrative of embodiments of the present invention, as described above, and they are not meant to limit the invention in any way. EXAMPLES
Example 1. Manufacture of starch nanoparticles
Potato starch was dispersed in RO water to obtain a 10 wt% aqueous dispersion, calculated by dry substance. The dispersion was mixed in a Waring blender to obtain homogenous slurry. The pH of the dispersion was 6.1, thus no pH adjustment was needed. The slurry was poured in to a microfluidizer M 110EH (equipped with an auxiliary processing module (APM, channel 200 μιη), and diamond interactions chambers (channel 100 μιη, channel 87 μιη, or channel 75 μιη), for effecting high- pressure homogenization. The slurry was in the first step fluidized under high shear, under a pressure of 1850 bar or 2050 bar and at the temperature above 30°C to effect gelatinization whereby gelatinized slurry was obtained. A heat exchanger was used for controlling the temperature of the output slurry in the range of 10-15°C. Said slurry was diluted with RO water to a consistency of 5 wt%, calculated based on dry matter. In the second step said diluted gelatinized slurry was subjected to homogenization (in the same apparatus as in the first step) under a pressure of 1850 bar or 2050 bar and at the temperature of 10-15°C, where practically no gelatinization took place. Under the constant pressure the slurry passed through the interaction chambers and nano- sized material was obtained. The homogenization at 10-15°C was repeated and total of passes was 18. The homogenized slurry was transparent. The material was subjected to freeze-drying to obtain a powdery product.
The nanostructure of the particles of the product was confirmed by particle size analysis (Beckman Coulter LS230 Laser Diffraction Particle Size Analyzer or Beckman Coulter N5 Laser Diffraction Particle Size Analyzer) and SEM .
The obtained starch nanoparticles had a specific surface area of 15-30 m2/g, and is based on laser diffraction using samples in wet state. In the laser diffraction method the particle size distributions of the dispersions are characterized by laser diffraction
(Coulter LS230, Beckman Coulter, CA) using refractive indices 1.53 and 1.333 for particles and water, respectively. Two replicate samples were analysed in two consecutive measurements, of which the average geometric volume distributions, the standard deviation for mean value and the specific surface area were calculated.
Specific surface area was also measured from dry samples using BET determination based on physical absorption of gas molecules on solid surface, giving the value 0.04085 m2/g- It was noticed that agglomeration of the particles took place, which affected the results obtained with BET.
In Figure 1 particle size distributions are shown, of native potato starch (Fig. la), and nanostarch manufactured from native potato starch diluted to 10 wt% consistency with respect to dry matter and gelatinized, followed by diluting the gelatinized slurry to 5 % consistency calculated based on dry matter and subjecting to 18 passes in the fluidizer (Fig. lb), as instructed in Example 1.
SEM images of the starch nanoparticles obtained in Example 1 are presented in Figures 2a (2 passes) and 2b (12 passes). Example 2. Manufacture of starch nanoparticles
Potato starch was dispersed in an aqueous mixture of ion-exchanged water containing 1 % by volume of ethanol to obtain a 10 wt% aqueous dispersion, calculated by dry substance. The dispersion was mixed in a blender to obtain homogenous slurry. No pH adjustment was needed. The slurry was poured in to a microfluidizer M l lOEH for effecting high-pressure homogenization. The slurry was in the first step fluidized for two passes under high shear, under a pressure of 1850 bar or 2050 bar and at the temperature above 30°C to effect gelatinization whereby gelatinized slurry was obtained. A heat exchanger was used for controlling the temperature of the output slurry in the range of 40-45°C after the first pass and 19°C after the second pass. Said slurry was diluted with ion-exchanged water to a consistency of 5 wt%, calculated based on dry matter. In the second step said diluted slurry was subjected to second fluidization (in the same apparatus as in the first step) under a pressure of 1850 bar
or 2050 bar and at the temperature of 10-15°C, where practically no gelatinization took place. A heat exchanger was used for controlling the temperature of the output slurry in the range of 13-15°C after each following pass. Under the constant pressure the slurry passed through the interaction chambers and nano-sized material was obtained, said slurry having pH of 6.8-6.9. The fluidization at 13-15°C was repeated and total of passes was 18. The obtained homogenized slurry was transparent. No significant change in the viscosity of the samples was observed after 3-18 passes, the viscosity was between 3 and 8 mPa*s when measured at the temperature of 21°C. The material was subjected to freeze-drying to obtain a powdery product. Viscosity of the homogenized slurry after 2, 6, 12, 15 and 18 passes is presented in Figure 3.
Example 3. Film formation of starch nanoparticles
A transparent and clear dispersion containing 1 wt% of native starch nanoparticles in water was evenly cast on a glass support and another dispersion containing 5 wt% of modified starch nanoparticles in acetone was evenly cast on a glass support, followed by drying at RT (approx. 20°C) for 24 hours. A solvent casting method was used. The films were formed readily and evenly. The films were removed from the supports and assessed visually and by microscope.
While the invention has been described with respect to specific examples presented in the figures, including presently preferred modes of carrying out the invention, those skilled in the art will appreciate that there are numerous variations and permutations of the above described embodiments that fall within the spirit and scope of the invention. It should be understood that the invention is not limited in its application to the details of construction and arrangements of the components set forth herein. Variations and modifications of the foregoing are within the scope of the present invention.
Claims
A process for the manufacture of starch nanoparticles, characterized in that the process comprises the steps, where in the first step starch is dispersed in an aqueous medium to obtain an aqueous dispersion, which is subjected to homogenization at a temperature between 30 and 80°C to yield a gelatinized slurry, in the second step aqueous medium is added to the gelatinized slurry in a volumetric ratio of 1 : 1 or more to obtain diluted gelatinized slurry and homogenizing the diluted gelatinized slurry at the temperature of 3-20°C for 1 to 30 passes to obtain starch nanoparticles.
The process according to claim 1, characterized in that in the first step the homogenization is carried out for 1-3 passes, preferably one pass.
The process according to claim 1 or 2, characterized in that in the first step the homogenization is carried at the temperature of 40-75°C, preferably 50-75°C.
The process according to any one of claims 1 - 3, characterized in that the gelatinized slurry is homogenized at the temperature of 3-20°C, preferably 8-18°C.
The process according to any one of claims 1 - 4, characterized in that the diluted gelatinized slurry has starch content between 0.01 and 10 wt%, preferably 0.1-7 wt%.
The process according to any one of claims 1 - 5, characterized in that the diluted gelatinized slurry is homogenized for 2-18 passes, preferably for 2-9 passes.
The process according to any one of claims 1 - 6, characterized in that the diluted gelatinized slurry is homogenized at the temperature of 8-18°C, preferably 10-15°C.
The process according to any one of claims 1 - 7, characterized in that in the first step 0.1 - 20 % by weight, preferably 0.5 - 15 % by weight, particularly preferably 2 - 10 % by weight of starch is dispersed in the aqueous medium.
The process according to any one of claims 1 - 8, characterized in that in the second step the homogenization of the diluted gelatinized slurry is carried out for 2-18 passes, preferably for 2-9 passes.
10. The process according to any one of claims 1 - 9, characterized in that the starch is selected from native starches, modified starches and combinations thereof.
11. The process according to any one of claims 1 - 10, characterized in that the native starch is selected from rice starch, wheat starch, barley starch, tapioca starch, maize starch, potato starch, cassava starch, fava starch, lentila starch, mung bean starch, pea starch, chickpea starch, acors starch, arrowroot starch, arracacha starch, bananas starch, beadfruit starch, buckwheat starch, canna starch, colacasia starch, katakuri starch, kudzu starch, malanga starch, millet starch, oats starch, oca starch, Polynesian arrowroot starch, sago starch, sorghum starch, sweet potatoe starch, rye starch, taro starch, chesnut starch, water chesnut starch, yams starch, preferably the native starch is selected from potato starch, corn starch, barley starch, wheat starch, tapioca starch, bean starch and rice starch.
12. The process according to any one of claims 1 - 10, characterized in that the modified starch is selected from cationic starches, anionic starches, thermoplastic starches, starch esters and starch ethers, preferably the modified starch is cationic potato starch.
13. The process according to any one of claims 1 - 12, characterized in that the aqueous medium is selected from water and mixtures of water with a C1-C4 alcohol or acetone or methyl ethyl ketone or with combinations thereof.
14. The process according to any one of claims 1 - 13, characterized in that the nanostarch slurry is subjected to drying.
15. The process according to claim 14, characterized in that the said drying is carried out as spray-drying, drying under vacuum, drying with heat, or as freeze-drying.
16. Starch nanoparticles, characterized in that said nanoparticles have average particle size less than 1 μιη and the cone and plate viscosity of an aqueous dispersion of said nanostarch particles is 1-100 mPa*s and the specific surface area of the starch nanoparticles is 10-70 m2/g, where the viscosity is measured using 5 wt% sample content and the temperature of 21°C.
17. The starch nanoparticles according to claim 16, characterized in that the average particle size is not more than 200 nm, preferably 20-100 nm.
18. The starch nanoparticles according to claim 16 or 17, characterized in that the cone and plate viscosity of an aqueous dispersion of said nanostarch particles is 2-80 mPa*s, preferably 2-50 mPa*s, particularly preferably 2-10 mPa*s, measured using 5 wt% sample content and the temperature of 21°C.
19. The starch nanoparticles according to any one of claims 16 - 18, characterized in that the starch is selected from native starches, modified starches and combinations thereof.
20. The starch nanoparticles according to claim 19, characterized in that the native starch is selected from rice starch, wheat starch, barley starch, tapioca starch, maize starch, potato starch, cassava starch, fava starch, lentila starch, mung bean starch, pea starch, chickpea starch, acors starch, arrowroot starch, arracacha starch, bananas starch, beadfruit starch, buckwheat starch, canna starch, colacasia starch, katakuri starch, kudzu starch, malanga starch, millet starch, oats starch, oca starch, Polynesian arrowroot starch, sago starch, sorghum starch, sweet potatoe starch, rye starch, taro starch, chesnut starch, water chesnut starch, yams starch, preferably the native starch is selected from potato starch, corn starch, barley starch, wheat starch, tapioca starch, bean starch and rice starch.
21. Starch nanoparticles according to claim 19, characterized in that the modified starch is selected from cationic starches, anionic starches, thermoplastic starches, starch esters and starch ethers, preferably the modified starch is cationic potato starch.
22. The starch nanoparticles according to any one of claims 16 - 21, characterized in that the starch nanoparticles are manufactured with the process according to any one of claims 1 - 15.
23. Use of the starch nanoparticles of any one of claims 16 - 22 or obtainable with the process of any one of claims 1 - 15 in barrier dispersions, pigments, films, flocculants, rheology modifiers, glues, adhesives, dispersion agents, thermoplastics, composites, water purification applications, cosmetics, pharmaceutical formulations, encapsulation agents, retention aids, sizing agents, fixatives, cleaning agents, and detergents.
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CN108018739A (en) * | 2017-12-14 | 2018-05-11 | 广东省造纸研究所 | A kind of nano-starch adhesive and preparation method thereof |
CN108913070A (en) * | 2018-05-21 | 2018-11-30 | 南京林业大学 | The preparation method and applications method of thermosetting property watersoluble melamine formaldehyde resin nano-powder adhesive |
RU2764638C2 (en) * | 2017-05-16 | 2022-01-19 | Рокетт Фрер | Stabilized buckwheat starch with “clean label” |
CN114729160A (en) * | 2019-11-08 | 2022-07-08 | 罗盖特公司 | Use of starch octenylsuccinate as a binder in wet granulation |
CN114806261A (en) * | 2022-04-18 | 2022-07-29 | 广东红日星实业有限公司 | Deinking agent and preparation method and application thereof |
CN115052904A (en) * | 2019-12-12 | 2022-09-13 | 阿彻丹尼尔斯米德兰公司 | Ultrafine starch or grain-based flour compositions and related methods |
CN117259772A (en) * | 2023-08-25 | 2023-12-22 | 江苏农林职业技术学院 | Radix puerariae nano-silver composite hydrosol and preparation method and application thereof |
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DE102016106852B4 (en) | 2016-04-13 | 2019-01-17 | Delfortgroup Ag | Packaging paper for food and related manufacturing process |
DE102016106852A1 (en) * | 2016-04-13 | 2017-10-19 | Delfortgroup Ag | Lightweight packaging paper for food with improved resistance to fats |
US10760219B2 (en) | 2016-04-13 | 2020-09-01 | Delfortgroup Ag | Light packaging paper for food having improved resistance to fats |
RU2764638C2 (en) * | 2017-05-16 | 2022-01-19 | Рокетт Фрер | Stabilized buckwheat starch with “clean label” |
CN108018739A (en) * | 2017-12-14 | 2018-05-11 | 广东省造纸研究所 | A kind of nano-starch adhesive and preparation method thereof |
CN108913070A (en) * | 2018-05-21 | 2018-11-30 | 南京林业大学 | The preparation method and applications method of thermosetting property watersoluble melamine formaldehyde resin nano-powder adhesive |
CN108913070B (en) * | 2018-05-21 | 2020-11-06 | 南京林业大学 | Preparation method and application method of thermosetting water-soluble melamine formaldehyde resin nano powder adhesive |
CN114729160A (en) * | 2019-11-08 | 2022-07-08 | 罗盖特公司 | Use of starch octenylsuccinate as a binder in wet granulation |
CN115052904A (en) * | 2019-12-12 | 2022-09-13 | 阿彻丹尼尔斯米德兰公司 | Ultrafine starch or grain-based flour compositions and related methods |
CN114806261A (en) * | 2022-04-18 | 2022-07-29 | 广东红日星实业有限公司 | Deinking agent and preparation method and application thereof |
CN114806261B (en) * | 2022-04-18 | 2023-04-11 | 广东红日星实业有限公司 | Deinking agent and preparation method and application thereof |
CN117259772A (en) * | 2023-08-25 | 2023-12-22 | 江苏农林职业技术学院 | Radix puerariae nano-silver composite hydrosol and preparation method and application thereof |
CN117259772B (en) * | 2023-08-25 | 2024-05-10 | 江苏农林职业技术学院 | Radix puerariae nano-silver composite hydrosol and preparation method and application thereof |
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