WO2005113616A2 - Melange amidon-polyester obtenu par extrusion reactive - Google Patents
Melange amidon-polyester obtenu par extrusion reactive Download PDFInfo
- Publication number
- WO2005113616A2 WO2005113616A2 PCT/US2005/015377 US2005015377W WO2005113616A2 WO 2005113616 A2 WO2005113616 A2 WO 2005113616A2 US 2005015377 W US2005015377 W US 2005015377W WO 2005113616 A2 WO2005113616 A2 WO 2005113616A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester
- blend
- containing polymer
- hydroxyl containing
- starch
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 229920002472 Starch Polymers 0.000 title claims abstract description 41
- 238000001125 extrusion Methods 0.000 title claims abstract description 35
- 239000008107 starch Substances 0.000 title claims abstract description 34
- 235000019698 starch Nutrition 0.000 title claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 56
- 229920000642 polymer Polymers 0.000 claims abstract description 51
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 31
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 28
- 239000004014 plasticizer Substances 0.000 claims abstract description 17
- 239000012802 nanoclay Substances 0.000 claims abstract description 14
- 150000002892 organic cations Chemical group 0.000 claims abstract description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000004927 clay Substances 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 150000002978 peroxides Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001254 oxidized starch Substances 0.000 claims description 7
- 235000013808 oxidized starch Nutrition 0.000 claims description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 229920000229 biodegradable polyester Polymers 0.000 claims description 4
- 239000004622 biodegradable polyester Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- -1 e.g. Polymers 0.000 abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000856 Amylose Polymers 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229940100445 wheat starch Drugs 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920002261 Corn starch Polymers 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000945 Amylopectin Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- XBGNERSKEKDZDS-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]acridine-4-carboxamide Chemical compound C1=CC=C2N=C3C(C(=O)NCCN(C)C)=CC=CC3=CC2=C1 XBGNERSKEKDZDS-UHFFFAOYSA-N 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 238000000692 Student's t-test Methods 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004633 polyglycolic acid Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229910000275 saponite Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012353 t test Methods 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- 241001517013 Calidris pugnax Species 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019759 Maize starch Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SZORMCBRRGPWKG-UHFFFAOYSA-N butanoic acid;pentanoic acid Chemical compound CCCC(O)=O.CCCCC(O)=O SZORMCBRRGPWKG-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 235000011868 grain product Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002525 ultrasonication Methods 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
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/10—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Definitions
- the invention is directed to starch or other hydroxyl containing polymer blend with polyester, of improved mechanical properties.
- One embodiment herein is directed at a hydroxyl containing polymer-polyester blend comprising plasticized oxidized hydroxyl containing polymer crosslinked with polyester, the blend having maximum tensile strength greater than elongation at break greater than 50% of that of the polyester.
- Another embodiment herein is directed at a method for preparing blend of hydroxyl containing polymer and polyester, of maximum tensile strength greater than 25%) of that of the polyester, Young's modulus greater than 25%> of that of the polyester and elongation at break greater than 50% of that of the polyester comprising the steps of (a) forming an admixture of hydroxyl containing polymer and polyester in a hydroxyl containing polymer-polyester weight ratio ranging from 1 :10 to 10:1, plasticizer in a hydroxyl containing polymer weight ratio ranging from 1 : 10 to 1:1 and H 2 0 2 in an amount effective to oxidize the hydroxyl containing polymer, and (b) feeding the admixture into an extruder and extruding therein or therethrough to cause oxidation of the hydroxyl containing polymer to form oxidized hydroxyl containing polymer and cause crosslinking between oxidized hydroxyl containing polymer and polyester of the admixture.
- the maximum tensile strength data in MPa set forth herein is determined by ASTM Test D638-96.
- the Young's modulus data in MPa set forth herein is determined by ASTM Test D638-96.
- the ultimate elongation data (%), i.e., elongation at break data (%) set forth herein, is determined by ASTM Test D638-96.
- FIG. 1A is a graph of wt % organoclay versus Youngs Modulus and shows results of Working Example I.
- FIG. 1 B is a graph of wt % organoclay versus elongation at break and shows results of Working Example I.
- FIG. 1C is a graph of wt % organoclay versus maximum tensile strength and shows results of Working Example I.
- the hydroxyl-containing polymer is preferably starch (e.g., wheat starch, high amylose corn starch, waxy maize starch and their blends).
- the starch can also be obtained, for example, from rice, potato, peas and/or tapioca.
- Native wheat and corn starches which are preferred for use herein, contain about 75% amylopectin fraction and 25% amylose fraction where the amylose fraction has a degree of polymerization (DP) ranging from lxlO 2 to 4x10 5 and the amylopectin fraction has a DP ranging from lxlO 4 to 4x10 7 , with branches after every 19-25 linear units.
- DP degree of polymerization
- the hydroxyl containing polymer can also be, for example, cellulosic polymer (M n ranging from 160,000 to 500,000,000 g/mol as determined by gel permeation chromatography or intrinsic viscosity measurements) or polyvinyl alcohol (M n ranging from 25,000 to 300,000 g/mol as determined by gel permeation chromatography).
- the oxidation converts the hydroxy of the hydroxyl containing polymer to carboxyl, aldehyde and ketone and fosters crosslinking by abstraction of hydrogen atoms adjacent to carbonyl on both oxidized hydroxyl containing polymer and polyester.
- the plasticizer is present to facilitate forming hydroxyl containing polymer melts during preparation processing without significant molecular breakdown.
- the plasticizer is a trihydric alcohol, very preferably glycerol.
- suitable plasticizers include monohydric, dihydric and polyhydric alcohols. Some examples are ethylene glycol, propylene glycol, erythritol, pentaerythritol, sorbitol and higher molecular weight plasticizers such as polyglycerol. Plasticizers used herein may also act as substrates in the oxidation/crosslinking pathways.
- the polyester is preferably a biodegradable polyester and when such polyester is used in a blend with oxidized starch or native starch (with or without clay), the blend is biodegradable.
- Biodegradable polyesters for use herein include, for example, polycaprolactone (e.g., poly (e-caprolactone), denoted PCL, polybutylene succinate, denoted PBS, polytetramethylene adipate-co-terephthalate (PAT), polyhydroxyl butyrate-valerate (PHBV), polylactic acid (PLA) and polyglycolic acid (PGA).
- the polyester can also be a non4?iodegradable polyester, e.g., polyethylene terephthalate.
- the polyesters typically have M n ranging from 40,000 to 300,000 g/mol as determined by gel permeation chromatography using polystyrene standards.
- the blend comprises glycerol plasticized oxidized starch crosslinked with polyester.
- the blend can optionally contain nanoclay modified to contain organic cation. Suitable nanoclays include montmorillonite, hectorite and saponite modified to contain organic cation.
- a preferred clay ingredient is montmorillonite modified to contain quaternary ammonium octadecyl cations (C18H 35 NH ). The clay functions to allow reduction in temperature during preparation processing, for obtaining the stated mechanical properties.
- the blend is preferably formulated from (A) 9 to 91 weight percent hydroxyl containing polymer and (B) from 91 to 9 weight percent polyester, based on (A) plus (B) being 100%; very preferably is formulated from (A) 10 to 95 weight percent plasticized hydroxyl containing polymer and (B) 90 to 5 weight percent polyester, based on (A) and (B) being 100%.
- the hydroxyl-containing polymer: plasticizer weight ratio can range, for example, from 10:1 to 1 :1 ; 2:1 is used in Working Example I.
- the blend is additionally formulated to contain from 0.5 to 10%, preferably more than 1%, nanoclay modified to contain organic cation, based on the weight of the blend including the organic cation modified clay.
- the second embodiment of the invention which is directed to preparing hydroxyl containing polymer-polyester blend of maximum tensile strength greater than 25%> of that of the polyester, Young's modulus greater than 25% of that of the polyester and elongation at break greater than 50% of that of the polyester, comprising the steps of (a) forming an admixture of hydroxyl containing polymer, plasticizer in a hydroxyl containing polymer plasticizer weight ratio ranging from 10:1 to 1 :1, polyester in a hydroxyl containing polymer: polyester weight ratio ranging from 1 : 10 to 10:1 and H 0 in an amount effective to oxidize the hydroxyl containing polymer, and (b) feeding the admixture into an extruder and extruding the admixture therein or therethrough to cause oxidation of the hydroxyl containing polymer to form oxidized hydroxyl containing polymer and cause crosslinking between oxidized hydroxyl containing polymer and polyester of the admixture.
- the hydroxyl containing polymers, plasticizers and polyesters are those of the first embodiment.
- the hydroxyl containing polymer is native wheat starch
- the plasticizer is glycerol
- the polyester is polycaprolactone (M n of 80,000) or polytetramethylene adipate- co-terephthalate. (high molecular weight, Eastar Bio Ultra)
- the blends are useful as plastic substitutes.
- the hydroxy containing polymer: polyester weight ratio ranges from 1: 10 to 10:1
- the hydroxyl-containing polyme ⁇ plasticizer weight ratio ranges from 10:1 to 1 :1
- the H 0 can be present in amount ranging from 0.01 ml/gm of hydroxyl containing polymer to 0.36 ml/gm of hydroxyl containing polymer on a 30% H 0 solution in water basis.
- the admixture for step (a) of the second embodiment can optionally include ferrous ions, e.g., in the form of ferrous sulfate, to catalyze the oxidation, e.g., in an amount of 0.0069-1.5 g/ml of peroxide (30%) solution in water basis); cupric ion, e.g., in the form of cupric sulfate is also optionally included to catalyze oxidation and decrease molecular weight of oxidized starch (by a pathway called the Ruff degradation pathway) but is omitted in applications requiring contact with food materials. When cupric sulfate is included, it is used in an amount of 0.0020-0.0125 g/gram starch.
- transition metal catalysts like iron, can replace copper.
- the H 0 2 and the catalysts perform a dual role, generating free hydroxyl radicals (i) for hydroxyl containing polymer oxidation and (ii) for causing crosslinking of oxidized starch and polyester.
- Nanoclay e.g., montmorillonite, hectorite or saponite, modified to contain an organic cation, e.g., montmorillonite modified to contain C
- Step (b) can be carried out in a batch extruding step or in a single continuous reactive extrusion process where oxidation and crosslinking successively occur.
- reactive extrusion is used herein to mean extrusion of plasticized hydroxyl containing polymer and polyester blend in the presence of hydrogen peroxide and catalyst(s) with or without clay.
- the extrusion temperature generally ranges from 90°C to 150°C but clay is a necessary ingredient to obtain the stated mechanical properties if the extrusion temperature is less than 130°C. There is no significant effect on properties when higher temperatures (130° C or higher) are used with clay.
- the plasticizer facilitates forming hydroxyl containing polymer, e.g., starch, melts during extrusion without significant molecular breakdown.
- the plasticizer may also act as a substrate for oxidation/crosslinking pathways during extrusion.
- the final products obtained which are embraced by the first embodiment of the invention herein are, for example, mixtures of starch, oxidized starch, glycerol, polycaprolactone and crosslinked oxidized starch-polycaprolactone.
- the invention is further described in Kalambur, S.B.
- the starch was native wheat starch (MIDSOL 50, Midwest Grain Products, Atchison, Kansas).
- the organoclay was Nanocor I.30E (montmorillonite) type with sodium cations, modified to replace sodium cations with quaternary ammonium octadecyl cations (C 1 8H35NH ).
- Ingredients were pre-mixed and fed to a co-rotating twin-screw microextruder (DACA Instruments, Goleta, California). The residence time was kept at 3 minutes. Melt was extruded out of the die of the microextruder in the form of cylindrical strands.
- the temperature throughout the extruder was maintained at 120°C. Screw speed was maintained at 125-130 rpm.
- the extruder barrel was blanketed with nitrogen during extrusion. Two batches of each formulation were extruded to ensure reproducibility.
- the extruded strands were injection molded in a micro-injector (DACA Instruments, Goleta, California) at 80-1 10 psi and 120°C in the form of dog-bone pieces of area of 1.5 x 4 mm 2 .
- the mold was maintained at ambient temperature. The conditions were such as to obtain peroxide oxidation to almost 100% conversion because of high temperature (120° C) during the reactive extrusion process.
- Relative crystallinity that is the heading of the right hand column of Table 4 is a measure of change in PCL crystallinity of PCL in starch-PCL blend compared to 100% PCL (relative crystallinity of 1.0)
- crystallization temperature in blends subjected to reactive extrusion increased as the amount of organoclay increased from 1 to 9% but were lower than that of blend without organoclay not subjected to reactive extrusion and also compared to 100% PCL.
- percent crystallinity increased with increasing organoclay content for the compositions obtained by reactive extrusion. The differences, however, were small.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
L'invention concerne un mélange de polymère contenant de l'hydroxyle, de l'amidon par exemple, et de polyester, du polycaprolactone par exemple. Ce mélange contient un polymère contenant de l'hydroxyle oxydé et plastifié, réticulé avec du polyester, et il présente des propriétés d'allongement à la rupture supérieures à 50 % de celles du polyester. Ledit mélange est obtenu par le mélange d'un polymère contenant de hydroxyle, de polyester, d'un plastifiant et de H2O2, puis par extrusion réactive de ce mélange. L'introduction de nanoargile modifiée au moyen d'un cation organique permet d'utiliser une température d'extrusion inférieure pour obtenir le même allongement à la rupture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56764604P | 2004-05-04 | 2004-05-04 | |
| US60/567,646 | 2004-05-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2005113616A2 true WO2005113616A2 (fr) | 2005-12-01 |
| WO2005113616A3 WO2005113616A3 (fr) | 2006-03-16 |
Family
ID=35428920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2005/015377 WO2005113616A2 (fr) | 2004-05-04 | 2005-05-04 | Melange amidon-polyester obtenu par extrusion reactive |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2005113616A2 (fr) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7998888B2 (en) | 2008-03-28 | 2011-08-16 | Kimberly-Clark Worldwide, Inc. | Thermoplastic starch for use in melt-extruded substrates |
| US8147965B2 (en) | 2008-05-14 | 2012-04-03 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing thermoplastic polyurethane |
| US8188185B2 (en) | 2008-06-30 | 2012-05-29 | Kimberly-Clark Worldwide, Inc. | Biodegradable packaging film |
| US8227658B2 (en) | 2007-12-14 | 2012-07-24 | Kimberly-Clark Worldwide, Inc | Film formed from a blend of biodegradable aliphatic-aromatic copolyesters |
| US8283006B2 (en) | 2008-12-18 | 2012-10-09 | Kimberly-Clark Worldwide, Inc. | Injection molding material containing starch and plant protein |
| US8329601B2 (en) | 2008-12-18 | 2012-12-11 | Kimberly-Clark Worldwide, Inc. | Biodegradable and renewable film |
| US8334327B2 (en) | 2006-08-31 | 2012-12-18 | Kimberly-Clark Worldwide, Inc. | Highly breathable biodegradable films |
| US8338508B2 (en) | 2008-05-14 | 2012-12-25 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
| US8759279B2 (en) | 2008-06-30 | 2014-06-24 | Kimberly-Clark Worldwide, Inc. | Fragranced biodegradable film |
| US8927617B2 (en) | 2008-06-30 | 2015-01-06 | Kimberly-Clark Worldwide, Inc. | Fragranced water-sensitive film |
| US10689566B2 (en) | 2015-11-23 | 2020-06-23 | Anavo Technologies, Llc | Coated particles and methods of making and using the same |
| US10982013B2 (en) | 2014-06-02 | 2021-04-20 | Anavo Technologies, Llc | Modified biopolymers and methods of producing and using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1274603B (it) * | 1994-08-08 | 1997-07-18 | Novamont Spa | Materiali espansi plastici biodegradabili |
| JP2000109665A (ja) * | 1998-10-02 | 2000-04-18 | Nippon Shokuhin Kako Co Ltd | 有機物質含有生分解性組成物の製造方法 |
| US20020168518A1 (en) * | 2001-05-10 | 2002-11-14 | The Procter & Gamble Company | Fibers comprising starch and polymers |
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2005
- 2005-05-04 WO PCT/US2005/015377 patent/WO2005113616A2/fr active Application Filing
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| US8334327B2 (en) | 2006-08-31 | 2012-12-18 | Kimberly-Clark Worldwide, Inc. | Highly breathable biodegradable films |
| US8227658B2 (en) | 2007-12-14 | 2012-07-24 | Kimberly-Clark Worldwide, Inc | Film formed from a blend of biodegradable aliphatic-aromatic copolyesters |
| US9150699B2 (en) | 2007-12-14 | 2015-10-06 | Kimberly-Clark Worldwide, Inc. | Film formed from a blend of biodegradable aliphatic-aromatic copolyesters |
| US7998888B2 (en) | 2008-03-28 | 2011-08-16 | Kimberly-Clark Worldwide, Inc. | Thermoplastic starch for use in melt-extruded substrates |
| US8445110B2 (en) | 2008-05-14 | 2013-05-21 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing thermoplastic polyurethanes |
| US8147965B2 (en) | 2008-05-14 | 2012-04-03 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing thermoplastic polyurethane |
| US8338508B2 (en) | 2008-05-14 | 2012-12-25 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
| US8188185B2 (en) | 2008-06-30 | 2012-05-29 | Kimberly-Clark Worldwide, Inc. | Biodegradable packaging film |
| US8759279B2 (en) | 2008-06-30 | 2014-06-24 | Kimberly-Clark Worldwide, Inc. | Fragranced biodegradable film |
| US8927617B2 (en) | 2008-06-30 | 2015-01-06 | Kimberly-Clark Worldwide, Inc. | Fragranced water-sensitive film |
| US9617400B2 (en) | 2008-06-30 | 2017-04-11 | Kimberly-Clark Worldwide, Inc. | Fragranced water-sensitive film |
| US8329601B2 (en) | 2008-12-18 | 2012-12-11 | Kimberly-Clark Worldwide, Inc. | Biodegradable and renewable film |
| US8283006B2 (en) | 2008-12-18 | 2012-10-09 | Kimberly-Clark Worldwide, Inc. | Injection molding material containing starch and plant protein |
| US10982013B2 (en) | 2014-06-02 | 2021-04-20 | Anavo Technologies, Llc | Modified biopolymers and methods of producing and using the same |
| US10689566B2 (en) | 2015-11-23 | 2020-06-23 | Anavo Technologies, Llc | Coated particles and methods of making and using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005113616A3 (fr) | 2006-03-16 |
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