CN113980362A - Starch-based foaming composition and preparation method thereof - Google Patents
Starch-based foaming composition and preparation method thereof Download PDFInfo
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- CN113980362A CN113980362A CN202111313417.XA CN202111313417A CN113980362A CN 113980362 A CN113980362 A CN 113980362A CN 202111313417 A CN202111313417 A CN 202111313417A CN 113980362 A CN113980362 A CN 113980362A
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- Prior art keywords
- starch
- acid
- parts
- organic
- organic acid
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- 229920002472 Starch Polymers 0.000 title claims abstract description 84
- 239000008107 starch Substances 0.000 title claims abstract description 81
- 235000019698 starch Nutrition 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 238000005187 foaming Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title description 13
- 150000007524 organic acids Chemical class 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 16
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 16
- 239000000811 xylitol Substances 0.000 claims abstract description 16
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims abstract description 16
- 229960002675 xylitol Drugs 0.000 claims abstract description 16
- 235000010447 xylitol Nutrition 0.000 claims abstract description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 229920001610 polycaprolactone Polymers 0.000 claims description 13
- 239000004626 polylactic acid Substances 0.000 claims description 13
- 150000004645 aluminates Chemical class 0.000 claims description 12
- 229920002261 Corn starch Polymers 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000008120 corn starch Substances 0.000 claims description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 7
- 229920002961 polybutylene succinate Polymers 0.000 claims description 7
- 239000004631 polybutylene succinate Substances 0.000 claims description 7
- 229920001896 polybutyrate Polymers 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- -1 polybutylene succinate Polymers 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 5
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- 240000003183 Manihot esculenta Species 0.000 claims description 4
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001592 potato starch Polymers 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims 1
- 239000004014 plasticizer Substances 0.000 abstract description 6
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 16
- 239000004088 foaming agent Substances 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 239000001273 butane Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- HTWLBDAAVAXOSI-UHFFFAOYSA-N CC[Si](OC)(OC)OC(C)(C)CCCCNCCN Chemical compound CC[Si](OC)(OC)OC(C)(C)CCCCNCCN HTWLBDAAVAXOSI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- KNXNFEMPRRJNKP-UHFFFAOYSA-N dioctyl phosphono phosphate propan-2-ol titanium Chemical compound [Ti].CC(C)O.CCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCC.CCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCC.CCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCC KNXNFEMPRRJNKP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
- C08J2203/164—Perhalogenated unsaturated hydrocarbons, e.g. F2C=CF2
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a starch-based foaming composition which is prepared from the following raw materials in parts by weight: 100 parts of starch, 0.5-2 parts of nano silicon dioxide, 50-200 parts of degradable resin, 2-10 parts of coupling agent and 2-10 parts of organic acid oligomer, wherein the organic acid oligomer is prepared from organic dibasic acid or polybasic acid, dihydric alcohol and xylitol. According to the invention, based on the esterification reaction of hydroxyl on the surface of starch, a binary or polybasic organic acid copolymer with a specific chain length is designed, the organic acid is grafted on the surface of the starch to destroy the crystalline structure of the starch, so that the plasticity of the starch is improved, and the starch can be blended and compounded with degradable resin under the condition of not adding a plasticizer, so that the low-cost fully-degradable modified resin with excellent performance is prepared. The starch in the starch-based foaming composition provided by the invention can be uniformly distributed in matrix resin, and after the starch-based foaming composition is extruded into a sheet, the obtained product has excellent mechanical properties and foaming properties.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a starch-based foaming composition and a preparation method thereof.
Background
The environmental protection degradation of polymer materials has become the main development trend of civil polymers, especially disposable polymers in the future. The aliphatic polyester-based polymer material has good degradation performance, but has high cost and is not favorable for large-scale popularization and application. Although the cost of degradation can be reduced by adding inorganic mineral fillers such as talc and calcium carbonate, the inorganic fillers are not decomposed into environmentally-friendly small molecular substances after degradation of the degradable polymers, and the influence on the surrounding environment is difficult to evaluate in a short time. The fully degradable resin based on natural polymer materials such as starch does not have the problems, and the natural polymer materials based on starch have wide application space as long as the problems of starch plasticization and compatibility with the polymer materials can be solved well.
Chinese patent 201210068834.7 discloses a nano composite starch micro-foaming biodegradable material, which is composed of starch, biological enzyme, polyol ester, amino fatty acid, modified nano calcium, modified ethylene-vinyl acetate copolymer and foaming agent. Compared with the existing degradable plastic system, the cost is reduced by 40%, various performances such as wear resistance, toughness, rigidity, foamability and the like of the biodegradable material are improved, and the processing temperature of the material is reduced. The system of the invention contains ethylene-vinyl acetate copolymer, the biodegradability is controversial, and the performance index of the degradable material is not given. Chinese patent 201410333068.1 discloses a naturally degradable starch foaming material and its production process, which is prepared from starch, plant fiber, foaming assistant and demoulding assistant. The starch is used as a main raw material to be made into a disposable material, so that the prepared disposable article is used, but the performance characteristics of a starch degradation product are not given in the invention. Chinese patent 201710309478.6 discloses a completely biodegradable fiber-reinforced starch foamed tableware and its preparation method, the foamed tableware is divided into an inner layer and an outer layer, the outer layer is composed of cassava starch, biodegradable short fiber, biodegradable toughening agent, compatilizer, foaming agent, heat insulating agent and release agent. The components are stirred and mixed evenly, and after hot-press molding, a biodegradable film is sprayed to obtain the completely biodegradable fiber reinforced starch foamed tableware. The tableware prepared by the invention can replace disposable tableware such as polystyrene and the like, but the process is more complicated and is not easy to form on general equipment.
The core problem of starch plasticization is to destroy the crystalline structure of starch, so that the starch can be plasticized at a proper temperature and blended and extruded with conventional resin to prepare modified materials with different properties. The common plasticizer has the possibility of slow precipitation, so that the method for preparing the starch modified material with plasticity by adopting a non-plasticizer plasticizing method has very important significance.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a starch-based foaming composition and a preparation method thereof, wherein the starch-based foaming composition provided by the present invention has good mechanical properties and foaming properties.
The invention provides a starch-based foaming composition which is prepared from the following raw materials in parts by weight:
starch 100 parts
0.5-2 parts of nano silicon dioxide
50-200 parts of degradable resin
2-10 parts of coupling agent
2-10 parts of organic acid oligomer, wherein the organic acid oligomer is prepared from organic dibasic acid or polybasic acid, dihydric alcohol and xylitol.
Preferably, the molar ratio of the organic dibasic acid or polybasic acid to the dihydric alcohol to the xylitol is (1.2-1.5) 1: 0.01.
Preferably, the organic dibasic acid or polybasic acid is selected from one or more of citric acid, malic acid, tartaric acid, oxalic acid, succinic acid and adipic acid;
the dihydric alcohol is one or more selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, polylactic acid polyalcohol, poly epsilon-caprolactone polyalcohol, diethylene glycol, neopentyl glycol and 2-methyl-1, 3-propylene glycol.
Preferably, the polymerization degree of the organic acid oligomer is 2 to 10.
Preferably, the starch is selected from one or more of corn starch, potato starch, wheat starch and tapioca starch.
Preferably, the diameter of the nano silicon dioxide is 1-500 nanometers.
Preferably, the degradable resin is a synthetic degradable polyester material, preferably one or more of polylactic acid (PLA), adipic acid-terephthalic acid-butanediol copolymer (PBAT), polybutylene succinate (PBS), adipic acid-succinic acid-butanediol copolymer (PBSA), poly epsilon-caprolactone (PCL), and Polyhydroxyalkanoate (PHA).
Preferably, the coupling agent is one or more of a silane coupling agent, an aluminate coupling agent and a titanate coupling agent, and is preferably gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyldimethoxysilane (KH560), gamma- (methacryloyloxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH792), N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (DL602), trimethyl aluminate, triisopropyl aluminate, tribenzyl aluminate, isopropyltris (dioctylpyrophosphate) titanate (KR-38S), bis (dioctylpyrophosphate) ethylene titanate (KR-238S).
Preferably, the preparation method of the organic acid oligomer comprises the following steps:
mixing organic dibasic acid or polybasic acid, dihydric alcohol and xylitol, heating to react under stirring, and vacuum-removing water produced by reaction to obtain carboxyl-terminated organic acid oligomer.
The invention also provides a preparation method of the starch-based foaming composition, which comprises the following steps:
carrying out ball milling on starch, organic acid oligomer and nano silicon dioxide to obtain a mixture;
stirring and mixing the mixture at a high speed until the water content in the system is lower than 2%, adding degradable resin and a coupling agent, mixing and discharging;
extruding and granulating the product in a double-screw extruder, and extruding a foaming thick sheet in a foaming machine to obtain the starch-based foaming composition.
Compared with the prior art, the invention provides a starch-based foaming composition which is prepared from the following raw materials in parts by weight: 100 parts of starch, 0.5-2 parts of nano silicon dioxide, 50-200 parts of degradable resin, 2-10 parts of coupling agent and 2-10 parts of organic acid oligomer, wherein the organic acid oligomer is prepared from organic dibasic acid or polybasic acid, dihydric alcohol and xylitol. According to the invention, based on the esterification reaction of hydroxyl on the surface of starch, a binary or polybasic organic acid copolymer with a specific chain length is designed, the organic acid is grafted on the surface of the starch to destroy the crystalline structure of the starch, so that the plasticity of the starch is improved, and the starch can be blended and compounded with degradable resin under the condition of not adding a plasticizer, so that the low-cost fully-degradable modified resin with excellent performance is prepared. The starch in the starch-based foaming composition provided by the invention can be uniformly distributed in matrix resin, and after the starch-based foaming composition is extruded into a sheet, the obtained product has excellent mechanical properties and foaming properties.
Detailed Description
The invention provides a starch-based foaming composition which is prepared from the following raw materials in parts by weight:
starch 100 parts
0.5-2 parts of nano silicon dioxide
50-200 parts of degradable resin
2-10 parts of coupling agent
2-10 parts of organic acid oligomer, wherein the organic acid oligomer is prepared from organic dibasic acid or polybasic acid, dihydric alcohol and xylitol.
The starch-based foaming composition provided by the invention comprises starch, wherein the starch is selected from one or more of corn starch, potato starch, wheat starch and cassava starch.
The starch-based foaming composition provided by the invention also comprises 0.5-2 parts of nano silicon dioxide, preferably 0.5, 1.0, 1.5, 2.0, or any value between 0.5-2 parts. The diameter of the nano silicon dioxide is 1-500 nanometers, preferably 1, 5, 10, 50, 100, 200, 300, 400, 500 or any value between 1-500 nanometers.
The starch-based foaming composition provided by the invention further comprises 50-200 parts of degradable resin, preferably 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, or any value between 50-200 parts. In the invention, the degradable resin is a synthetic degradable polyester material, preferably one or more of polylactic acid (PLA), adipic acid-terephthalic acid-butanediol copolymer (PBAT), polybutylene succinate (PBS), adipic acid-succinic acid-butanediol copolymer (PBSA), poly epsilon-caprolactone (PCL) and Polyhydroxyalkanoate (PHA). Preferably one or more of PLA, PBS and PBAT, and the relative content of the degradable resin is adjusted according to the requirement on the mechanical property of the product
The starch-based foaming composition further comprises 2-10 parts of a coupling agent, preferably 2, 3, 4, 5, 6, 7, 8, 9, 10, or any value between 2-10 parts. The coupling agent is one or more of silane coupling agent, aluminate coupling agent and titanate coupling agent, preferably gamma-aminopropyl triethoxysilane (KH550), gamma-glycidoxypropyl dimethoxysilane (KH560), gamma- (methacryloyloxy) propyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethyl (ethyltrimethoxysilane) (KH792), N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane (DL602), trimethyl aluminate, triisopropyl aluminate, tribenzyl aluminate, isopropyl tri (dioctylpyrophosphate) titanate (KR-38S) or bis (dioctylpyrophosphate) ethylene titanate (KR-238S). The coupling agent can improve the compatibility of the starch and the degradable resin and improve the overall mechanical property of the blend. Among them, an aluminate coupling agent is preferable, and triisopropyl aluminate is particularly preferable.
The starch-based foaming composition further comprises 2-10 parts of organic acid oligomer, preferably 2, 3, 4, 5, 6, 7, 8, 9, 10, or any value between 2-10 parts.
In the present invention, the organic acid oligomer is prepared from an organic dibasic acid or polybasic acid, a dihydric alcohol and xylitol.
Preferably, the preparation method of the organic acid oligomer comprises the following steps:
mixing organic dibasic acid or polybasic acid, dihydric alcohol and xylitol, heating to react under stirring, and vacuum-removing water produced by reaction to obtain carboxyl-terminated organic acid oligomer.
Firstly, mixing organic dibasic acid or polybasic acid, dihydric alcohol and xylitol in a reaction kettle to obtain a mixture.
Wherein the molar ratio of the organic dibasic acid or polybasic acid to the dihydric alcohol to the xylitol is (1.2-1.5): 1:0.01, preferably 1.2:1:0.01, 1.3:1:0.01, 1.4:1:0.01, 1.5:1:0.01, or any value between (1.2-1.5): 1: 0.01.
The organic binary acid or the polybasic acid is selected from one or more of citric acid, malic acid, tartaric acid, oxalic acid, succinic acid and adipic acid;
the dihydric alcohol is one or more selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, polylactic acid polyalcohol, poly epsilon-caprolactone polyalcohol, diethylene glycol, neopentyl glycol and 2-methyl-1, 3-propylene glycol.
Wherein, the organic dibasic acid or polybasic acid is preferably citric acid or succinic acid; the diol is preferably 1, 4-butanediol, a polylactic acid polyol or a polyepsilon caprolactone polyol.
Then, the mixture is heated and reacted under the condition of stirring to obtain a reactant.
Wherein the reaction temperature is 90-150 ℃, preferably 90, 100, 110, 120, 130, 140, 150, or any value between 90-150 ℃, and the reaction time is 30-60 minutes, preferably 30, 40, 50, 60, or any value between 30-60 minutes.
Next, water produced by the reaction was removed in vacuo to give a carboxyl-terminated organic acid oligomer.
Wherein the polymerization degree of the organic acid oligomer is 2-10, preferably any value between 2, 3, 4, 5, 6, 7, 8, 9, 10, or 2-10 parts.
The invention also provides a preparation method of the starch-based foaming composition, which comprises the following steps:
carrying out ball milling on starch, organic acid oligomer and nano silicon dioxide, and discharging to obtain a mixture;
stirring and mixing the mixture at a high speed until the water content in the system is lower than 2%, adding degradable resin and a coupling agent, mixing and discharging;
extruding and granulating the product in a double-screw extruder, and extruding a foaming thick sheet in a foaming machine to obtain the starch-based foaming composition.
Firstly, carrying out ball milling on starch, organic acid oligomer and nano silicon dioxide, wherein the ball milling time is 30-120 min, preferably 30, 40, 50, 60, 70, 80, 90, 100, 110, 120 or any value between 30-120 min.
Discharging after ball milling is finished to obtain a mixture, and then stirring and mixing the mixture at a high speed until the water content in the system is lower than 2%, wherein the high-speed stirring is carried out in a high-speed stirrer, and the stirring temperature is 80-120 ℃, preferably 80, 90, 100, 110, 120, or any value between 80-120 ℃; the stirring time is 15-45 minutes, preferably 15, 20, 25, 30, 35, 40, 45 or any value between 15-45 minutes.
When the water content in the system is lower than 2%, adding the degradable resin and the coupling agent for mixing, wherein the mixing temperature is 80-120 ℃, and preferably any value between 80, 90, 100, 110 and 120, or between 80 and 120 ℃.
After mixing, the obtained product is granulated and then extruded into a foaming thick sheet in a foaming machine to obtain the starch-based foaming composition.
In the invention, a twin-screw extruder is preferably adopted for extrusion granulation at 130-180 ℃, and the extrusion granulation temperature is preferably 130, 140, 150, 160, 170, 180 or any value between 130-180 ℃.
And extruding the obtained particles into a foaming thick sheet by using a foaming agent in a foaming extruder at the temperature of 135-180 ℃, wherein the foaming agent is preferably 135-150 ℃, and the foaming agent is preferably one or more of supercritical carbon dioxide, butane, pentane and dichlorotetrafluoroethane.
In the invention, the starch-based foaming composition can be produced by adopting an extrusion foaming sheet, and a low-density and degradable product is prepared by adopting a thermal forming process, has higher rigidity and can be used for disposable food containers, fruit trays and the like.
According to the invention, based on the esterification reaction of hydroxyl on the surface of starch, a binary or polybasic organic acid copolymer with a specific chain length is designed, the organic acid is grafted on the surface of the starch to destroy the crystalline structure of the starch, so that the plasticity of the starch is improved, and the starch can be blended and compounded with degradable resin under the condition of not adding a plasticizer, so that the low-cost fully-degradable modified resin with excellent performance is prepared. The starch in the starch-based foaming composition provided by the invention can be uniformly distributed in matrix resin, and after the starch-based foaming composition is extruded into a sheet, the obtained product has excellent mechanical properties and foaming properties.
For further understanding of the present invention, the starch-based foaming composition and the preparation method thereof provided by the present invention are illustrated below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Comparative example 1
100 parts of corn starch and 1 part of coupling agent trimethyl aluminate are mixed in a high-speed stirrer at 120 ℃ for 40 minutes under the condition of 500 revolutions/minute until the water content is lower than 2 percent, 150 parts of polylactic acid and 50 parts of PBAT are added and mixed for 1 minute, and after discharging and cooling to room temperature, the mixture is added into a double-screw extruder and extruded and granulated at 170 ℃. The obtained particles were extruded into a foamed slab with a thickness of 4 cm in a foaming extruder at 160 ℃ using supercritical carbon dioxide as a foaming agent, and the compression strength of the sample was measured, and the results are shown in Table 1.
Comparative example 2
100 parts of corn starch and 30 parts of plasticizer glycerol are mixed for 40 minutes at 110 ℃ in a high-speed mixer under the condition of 1000 revolutions per minute until the water content is lower than 2 percent, 200 parts of PLA is added and mixed for 1 minute, the mixture is cooled to room temperature after discharging, and then the mixture is added into a double-screw extruder and extruded and granulated at 150 ℃. The resulting particles were extruded into foamed slabs in a foaming extruder at 150 ℃ with butane as the blowing agent, 4 cm in thickness, and the compressive strength of the samples was measured, the results of which are shown in Table 1.
Preparation example 1
In a reaction kettle provided with a stirring device and a thermometer, mixing the raw materials in a molar ratio of 1.5:1:0.01 respectively adding citric acid, 1, 4-butanediol and xylitol, heating to 150 ℃, reacting for 30 minutes, distilling under reduced pressure to remove water as a reaction by-product, discharging the product out of the reaction kettle to obtain an organic acid oligomer A with the polymerization degree of 150-200 for later use.
Preparation example 2
In a reaction kettle provided with a stirring device and a thermometer, mixing the raw materials in a molar ratio of 1.2:1:0.01 respectively adding malic acid, neopentyl glycol and xylitol, heating to 90 ℃, reacting for 60 minutes, distilling under reduced pressure to remove water as a reaction by-product, and discharging a product out of the reaction kettle to obtain an organic acid oligomer B with the polymerization degree of 100-150 for later use.
Preparation example 3
Tartaric acid, poly-epsilon-caprolactone polyol (with the polymerization degree of 8-12) and xylitol are respectively added into a reaction kettle with a stirring device and a thermometer according to the molar ratio of 1.3:1:0.1, the temperature is raised to 125 ℃, the reaction lasts for 45 minutes, water as a reaction by-product is removed by distillation under reduced pressure, and the product is discharged out of the reaction kettle to obtain organic acid oligomer C with the polymerization degree of 150-200 for later use.
Example 1
100 parts of corn starch, 2 parts of organic acid oligomer A and 2 parts of silicon dioxide are ball-milled in a ball mill for 120 minutes and discharged. And then transferring the mixture to a high stirring machine, mixing the mixture for 45 minutes at 80 ℃ until the water content in the system is lower than 2 percent, adding 50 parts of degradable resin PLA and 50 parts of silane coupling agent KH 5502 parts, mixing the mixture for 1 minute at 80 ℃, and discharging the mixture. The obtained product is extruded and granulated at 150 ℃ in a double-screw extruder, and then a foaming thick sheet is extruded at 160 ℃ in a foaming extruder by using supercritical carbon dioxide as a foaming agent, the thickness is 4 cm, and the compression strength of a sample is tested, and the result is shown in the attached table 1.
Example 2
100 parts of corn starch, 5 parts of organic acid oligomer B and 1 part of silicon dioxide are ball-milled in a ball mill for 60 minutes, and then the material is discharged. And then transferring the mixture into a high stirring machine, mixing the mixture for 30 minutes at 100 ℃ until the water content in the system is lower than 2%, adding 50 parts of degradable resin PLA 150 and PBAT and 5 parts of titanate coupling agent KR-38S, mixing the mixture for 1 minute at 100 ℃, and discharging the mixture. The obtained product is extruded and granulated at 150 ℃ in a double-screw extruder, then a foaming thick sheet is extruded at 140 ℃ in a foaming extruder by using butane as a foaming agent, the thickness is 4 cm, and the compression strength of a sample is tested, and the result is shown in the attached table 1.
Example 3
100 parts of corn starch, 10 parts of organic acid oligomer C and 2 parts of silicon dioxide are ball-milled in a ball mill for 30 minutes and then discharged. And transferring the mixture to a high stirring machine, mixing the mixture for 15 minutes at 120 ℃ until the water content in the system is lower than 2%, adding 120 parts of degradable resin PCL, 30 parts of PLA and 10 parts of triisopropyl aluminate, mixing the mixture for 1 minute at 120 ℃, and discharging the mixture. The obtained product is extruded and granulated at 180 ℃ in a double-screw extruder, then a foaming thick sheet is extruded at 155 ℃ in a foaming extruder by taking pentane as a foaming agent, the thickness is 4 cm, and the compression strength of a sample is tested, and the result is shown in the attached table 1.
Example 4
100 parts of corn starch, 5 parts of organic acid oligomer A and 2 parts of silicon dioxide are ball-milled in a ball mill for 40 minutes and discharged. And then transferring the mixture to a high stirring machine, mixing the mixture for 40 minutes at 90 ℃ until the water content in the system is lower than 2%, adding 130 parts of degradable resin PHA, 20 parts of PBSA, 3 parts of triisopropyl aluminate and 2 parts of titanate coupling agent KR-238S, mixing the mixture for 1 minute at 90 ℃, and then discharging the mixture. The resulting product was pelletized by extrusion at 175 ℃ in a twin-screw extruder and then extruded in a foaming extruder at 160 ℃ into foamed slabs 4 cm thick using a 1:1 mixture of butane and pentane as a blowing agent, and the compressive strength of the samples was measured, the results of which are shown in Table 1.
Example 5
100 parts of corn starch, 8 parts of organic acid oligomer B and 1 part of silicon dioxide are ball-milled in a ball mill for 90 minutes, and then the material is discharged. And then transferring the mixture to a high stirring machine, mixing the mixture for 40 minutes at 110 ℃ until the water content in the system is lower than 2%, adding 100 parts of degradable resin PLA, 20 parts of PCL, 1 part of trimethyl aluminate and 1 part of titanate coupling agent KR-38S, and mixing the mixture for 1 minute at 110 ℃ and then discharging the mixture. The resulting product was pelletized by extrusion at 145 ℃ in a twin-screw extruder, and then a foamed slab was extruded at 135 ℃ in a foaming extruder with dichlorotetrafluoroethane as a foaming agent, with a thickness of 4 cm, and the compressive strength of the sample was measured, and the results are shown in Table 1.
Example 6
100 parts of corn starch, 6 parts of organic acid oligomer C and 1 part of silicon dioxide are ball-milled in a ball mill for 110 minutes, and then the material is discharged. And then transferring the mixture to a high stirring machine, mixing the mixture for 40 minutes at 100 ℃ until the water content in the system is lower than 2%, adding 60 parts of degradable resin PLA, 10 parts of PBSA, 120 parts of PBAT and 2 parts of triisopropyl aluminate, mixing the mixture for 1 minute at 100 ℃, and then discharging the mixture. The obtained product is extruded and granulated at 155 ℃ in a double-screw extruder, and then a foaming thick sheet with the thickness of 4 cm is extruded at 140 ℃ in a foaming extruder by using supercritical carbon dioxide as a foaming agent, and the compression strength of a sample is tested, and the result is shown in table 1.
Table 1 results of mechanical property test of comparative examples and examples.
| Sample (I) | Expansion ratio | Compressive Strength (MPa) |
| Comparative example 1 | 3 | 0.5 |
| Comparative example 2 | 3 | 0.3 |
| Example 1 | 15 | 6.5 |
| Example 2 | 22 | 8.7 |
| Example 3 | 18 | 5.8 |
| Example 4 | 15 | 6.4 |
| Example 5 | 15 | 12.1 |
| Example 6 | 28 | 7.2 |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The starch-based foaming composition is characterized by comprising the following raw materials in parts by weight:
starch 100 parts
0.5-2 parts of nano silicon dioxide
50-200 parts of degradable resin
2-10 parts of coupling agent
2-10 parts of organic acid oligomer, wherein the organic acid oligomer is prepared from organic dibasic acid or polybasic acid, dihydric alcohol and xylitol.
2. The composition according to claim 1, wherein the molar ratio of the organic dibasic acid or polybasic acid, the dibasic alcohol and the xylitol is (1.2-1.5) to 1: 0.01.
3. The composition of claim 1, wherein the organic diacid or polyacid is selected from one or more of citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, adipic acid;
the dihydric alcohol is one or more selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, polylactic acid polyalcohol, poly epsilon-caprolactone polyalcohol, diethylene glycol, neopentyl glycol and 2-methyl-1, 3-propylene glycol.
4. The composition according to claim 1, wherein the organic acid oligomer has a degree of polymerization of 2 to 10.
5. The composition as claimed in claim 1, wherein the starch is selected from one or more of corn starch, potato starch, wheat starch, tapioca starch.
6. The composition of claim 1, wherein the nanosilica has a diameter of 1 to 500 nm.
7. The composition according to claim 1, wherein the degradable resin is a synthetic degradable polyester material, preferably one or more of polylactic acid (PLA), adipic acid-terephthalic acid-butanediol copolymer (PBAT), polybutylene succinate (PBS), adipic acid-succinic acid-butanediol copolymer (PBSA), poly epsilon-caprolactone (PCL), Polyhydroxyalkanoate (PHA).
8. The composition as claimed in claim 1, wherein the coupling agent is a silane coupling agent or an aluminate coupling agent, one or more of titanate coupling agents, preferably gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyldimethoxysilane (KH560), gamma- (methacryloyloxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH792), N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (DL602), trimethyl aluminate, triisopropyl aluminate, tribenzyl aluminate, isopropyltris (dioctylpyrophosphate) titanate (KR-38S), bis (dioctyloxypyrophosphate) ethylene titanate (KR-238S).
9. The composition of claim 1, wherein the organic acid oligomer is prepared by a process comprising the steps of:
mixing organic dibasic acid or polybasic acid, dihydric alcohol and xylitol, heating to react under stirring, and vacuum-removing water produced by reaction to obtain carboxyl-terminated organic acid oligomer.
10. A method of preparing a starch-based foaming composition according to any of claims 1 to 9, comprising the steps of:
carrying out ball milling on starch, organic acid oligomer and nano silicon dioxide to obtain a mixture;
stirring and mixing the mixture at a high speed until the water content in the system is lower than 2%, adding degradable resin and a coupling agent, mixing and discharging;
extruding and granulating the product in a double-screw extruder, and extruding a foaming thick sheet in a foaming machine to obtain the starch-based foaming composition.
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