CN114230744B - Starch-based elastomer and preparation method and application thereof - Google Patents
Starch-based elastomer and preparation method and application thereof Download PDFInfo
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- CN114230744B CN114230744B CN202210058916.7A CN202210058916A CN114230744B CN 114230744 B CN114230744 B CN 114230744B CN 202210058916 A CN202210058916 A CN 202210058916A CN 114230744 B CN114230744 B CN 114230744B
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- starch
- based elastomer
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- elastomer according
- modified starch
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- 229920002472 Starch Polymers 0.000 title claims abstract description 109
- 239000008107 starch Substances 0.000 title claims abstract description 109
- 235000019698 starch Nutrition 0.000 title claims abstract description 109
- 229920001971 elastomer Polymers 0.000 title claims abstract description 88
- 239000000806 elastomer Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000004368 Modified starch Substances 0.000 claims abstract description 52
- 229920000881 Modified starch Polymers 0.000 claims abstract description 52
- 235000019426 modified starch Nutrition 0.000 claims abstract description 52
- -1 polypropylene carbonate Polymers 0.000 claims abstract description 44
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 36
- 239000010902 straw Substances 0.000 claims abstract description 33
- 229920005862 polyol Polymers 0.000 claims abstract description 29
- 150000003077 polyols Chemical class 0.000 claims abstract description 29
- 229920000379 polypropylene carbonate Polymers 0.000 claims abstract description 29
- 150000002009 diols Chemical class 0.000 claims abstract description 28
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 30
- 239000003963 antioxidant agent Substances 0.000 claims description 29
- 239000004970 Chain extender Substances 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000004014 plasticizer Substances 0.000 claims description 23
- 230000003078 antioxidant effect Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 13
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000010008 shearing Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006065 biodegradation reaction Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000002505 iron Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- 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)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a starch-based elastomer, a preparation method and application thereof, comprising the following preparation raw materials: a polypropylene carbonate polyol, polycaprolactone diol, modified starch, straw, filler and auxiliary agent; wherein the modified starch is iron ion modified starch. The complex is formed by ferric ions and starch, and the coordination clusters formed by coordination reaction have physical crosslinking effect, so that the movement of starch molecular chains can be limited, the shearing viscosity of melt is improved, the reverse plasticization effect is realized, the extrusion residence time of the melt is prolonged, the shearing degradation effect of a screw is further improved to a certain extent, and the strength and the thermal stability of starch are improved. The elastomer prepared by the modified starch has good mechanical property and degradability.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a starch-based elastomer and a preparation method and application thereof.
Background
In order to reduce white pollution caused by high molecular products, development of new generation plastic and elastomer products which have excellent properties and are degradable is pursued at home and abroad. One of the materials is aliphatic polyester material, but the problems of high crystallinity, secondary crystallization and the like caused by high stereoregularity of the materials cause poor mechanical properties and narrow processing window; on the other hand, the price of aliphatic polyester is several times that of common high polymer material, and industrial production is difficult to realize before the price of aliphatic polyester is reduced on a large scale. And thermoplastic materials using natural polysaccharide macromolecules such as starch and the like as base materials, such as starch-based plastics plasticized by glycerol, ethylene glycol, sorbitol and the like, are degradable, but the mechanical properties of the materials are poor, and the application range is limited.
Therefore, there is a need to develop a starch-based elastomer which is degradable and has good mechanical properties.
Disclosure of Invention
The first technical problem to be solved by the invention is that: a starch-based elastomer which is degradable and has good mechanical properties.
The second technical problem to be solved by the invention is that: the preparation method of the starch-based elastomer.
The third technical problem to be solved by the invention is that: the use of the above starch-based elastomer.
In order to solve the first technical problem, the technical scheme provided by the invention is as follows: a starch-based elastomer comprising the following raw materials: a polypropylene carbonate polyol, polycaprolactone diol, modified starch, straw, filler and auxiliary agent;
wherein the modified starch is iron ion modified starch.
According to some embodiments of the invention, the auxiliary agents include chain extenders, catalysts, antioxidants, and plasticizers.
Chain extender is added in the processing course, and the molecular chain is unfolded and the molecular weight is increased by the poly propylene carbonate polyol and the polycaprolactone diol.
The antioxidant is added, so that the composite material has stable performance in daily transportation and use, and is not easy to age.
The plasticizer is inserted between starch molecular chains to increase the distance between the molecular chains, so that the Van der Waals force between the molecular chains is weakened, the macromolecular chains are easy to move, the glass transition temperature of the starch polymer is reduced, the plasticity is increased, and the starch is easy to process, so that the starch has thermoplastic processability.
According to some embodiments of the invention, the method comprises the following raw materials in parts by weight: 40-50 parts of polypropylene carbonate polyol; 10-25 parts of polycaprolactone diol; 10-25 parts of modified starch; 20-40 parts of straw; 1-5 parts of filler; 0.5 to 1 part of catalyst; 3-5 parts of antioxidant; 5-10 parts of chain extender and 1-3 parts of plasticizer.
According to some embodiments of the invention, the polypropylene carbonate polyol has a molecular weight of 2000 to 5000; preferably, the molecular weight of the polycaprolactone diol is between 1000 and 4000.
Too large molecular weight can affect the tensile strength and hardness of the elastomer, and can reduce the tensile strength and hardness; too small a molecular weight affects the elongation and permanent set of the elastomer, and deteriorates the elongation and permanent set properties.
According to some embodiments of the invention, the iron ion modified starch comprises starch and an iron salt.
According to some embodiments of the invention, the iron salt comprises an organic iron salt.
According to some embodiments of the invention, the organic iron salt comprises a carboxylate salt.
According to some embodiments of the invention, the iron ion modified starch comprises the following preparation raw materials in parts by weight:
1 part of starch and 2 to 3 parts of ferric salt.
According to some embodiments of the invention, the iron ion modified starch comprises the following preparation raw materials in parts by weight:
1 part of starch, 2 to 3 parts of ferric salt and 40 to 60 parts of water.
According to some embodiments of the invention, the method for preparing iron ion modified starch comprises the steps of:
preparing a starch solution, and adding the ferric salt into the starch solution for reaction.
According to some embodiments of the invention, the method of formulating a starch solution comprises the steps of:
adding the starch into the water, and uniformly mixing at 80-100 ℃ to obtain the starch.
According to some embodiments of the invention, the temperature of the reaction is 20 ℃ to 30 ℃.
According to some embodiments of the invention, the time of the method is 2h to 4h.
According to some embodiments of the invention, the filler comprises a nanofiller.
According to some embodiments of the invention, the nanofiller comprises at least one of nano titanium dioxide and nano zinc oxide.
The addition of the nano titanium dioxide and the nano zinc oxide has the self-cleaning and decontamination effects.
According to some embodiments of the invention, the nano titania is modified nano titania.
According to some embodiments of the invention, the modified nano titania is carboxylated nano titania.
According to some embodiments of the invention, the preparation of carboxylated nano titanium dioxide comprises the steps of:
s01, mixing n-butyl titanate, ethanol, citric acid and water, and regulating the pH value to 2-4 to obtain sol;
s02, reacting the sol for 2-4 hours at 60-80 ℃ under the protection of nitrogen, carrying out solid-liquid separation, collecting solid phase, and washing to obtain the carboxylated nano titanium dioxide.
According to some embodiments of the invention, the molar ratio of n-butyl titanate, ethanol, citric acid and water is 1: 30-100: 5-10: 0.5 to 4.
According to some embodiments of the invention, the nano zinc oxide is a modified nano zinc oxide.
According to some embodiments of the invention, the modified nano zinc oxide is an aminated zinc oxide.
According to some embodiments of the invention, the preparation of the aminated nano zinc oxide comprises the steps of:
s001, adding zinc acetate dihydrate into ethanol, refluxing for 1-2 h at 60-80 ℃, cooling to room temperature, adding KOH for reaction for 50-70 min, adding 3-aminopropyl triethoxysilane for reaction for 2-4 h, carrying out solid-liquid separation, collecting solid phase, and washing to obtain the amination nanometer zinc oxide.
According to some embodiments of the invention, the molar ratio of zinc acetate dihydrate, ethanol, KOH, and 3-aminopropyl triethoxysilane is 1: 30-100: 1.5 to 2.5:1 to 10.
The nanometer material is modified, and grafted to the main polymer body to disperse homogeneously in the elastomer.
According to some embodiments of the invention, the chain extender comprises at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
According to some embodiments of the invention, the catalyst comprises at least one of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, tin dioctanoate, and dibutyltin dilaurate.
According to some embodiments of the invention, the antioxidant comprises one of hindered phenolic antioxidants, hindered amine antioxidants, phosphite antioxidants, sulfur-containing synergists, benzofuranone derivatives.
According to some embodiments of the invention, the plasticizer comprises at least one of formamide, glycerol, and urea.
The starch-based elastomer according to the embodiment of the invention has at least the following beneficial effects: the complex is formed by ferric ions and starch, and the coordination clusters formed by coordination reaction have physical crosslinking effect, so that the movement of starch molecular chains can be limited, the shearing viscosity of melt is improved, the reverse plasticization effect is realized, the extrusion residence time of the melt is prolonged, the shearing degradation effect of a screw is further improved to a certain extent, and the strength and the thermal stability of starch are improved. The elastomer prepared by the modified starch has good mechanical property and degradability.
In order to solve the second technical problem, the technical scheme provided by the invention is as follows: the preparation method of the starch-based elastomer comprises the following steps:
s1, mixing modified starch and straw to form a premix;
s2, mixing the premix prepared in the step S1, the filler and the auxiliary agent, adding polycaprolactone diol and polypropylene carbonate polyol, and mixing again to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, and extruding and granulating to obtain the starch-based elastomer.
According to some embodiments of the invention, stirring is required during the mixing in step S1; the stirring speed is 200 rpm/min-400 rpm/min; the stirring time is 5-10 min.
According to some embodiments of the invention, stirring is required during the remixing in step S2; the stirring speed is 900 rpm/min-1100 rpm/min; the stirring time is 20-30 min.
According to some embodiments of the invention, the operating parameters of the twin-screw granulator in step S3 are:
the die head temperature of the double-screw granulator is 120-180 ℃; the rotating speed of the screw is 300 rpm/min-500 rpm/min; the vacuum degree is 0.04 Mpa-0.05 Mpa.
The preparation method of the starch-based elastomer according to the embodiment of the invention has at least the following beneficial effects: the preparation method provided by the invention is simple in process, and realizes the rapid preparation and mass production of the polyurethane elastomer.
In order to solve the third technical problem, the technical scheme provided by the invention is as follows: the application of the starch-based elastomer in preparing degradable materials.
The application according to the embodiment of the invention has at least the following beneficial effects: the invention utilizes the synergistic effect of the polypropylene carbonate polyol, the polycaprolactone diol and the modified starch, so that the starch-based elastomer has good microbial degradability and keeps good mechanical properties; after the starch-based elastomer is degraded for 90 days, the mass loss reaches 86.5%, and the elongation at break reaches more than 830%.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
The preparation method of carboxylated nano titanium dioxide selected in the embodiment of the invention comprises the following steps:
1 part by weight of n-butyl titanate is dissolved in 30 parts by weight of absolute ethyl alcohol, after magnetic stirring is carried out for 20min, 10 parts by weight of citric acid and 0.5 part by weight of water mixed solution are slowly added dropwise, the pH value is adjusted to 2, stable, uniform, clear and transparent pale yellow sol is obtained, heating and stirring reaction is carried out at 80 ℃ under the protection of nitrogen, and then suction filtration, washing and drying are carried out, thus obtaining carboxylated titanium dioxide.
The preparation method of the amination nanometer zinc oxide selected in the embodiment of the invention comprises the following steps:
adding 1 part by weight of zinc acetate dihydrate into 30 parts by weight of ethanol, refluxing at 80 ℃ for 2 hours, cooling to room temperature, adding 2 parts by weight of KOH for reaction for 60 minutes, adding 10 parts by weight of 3-aminopropyl triethoxysilane for reaction for 3 hours, centrifuging, and washing to obtain the aminated nano zinc oxide.
The preparation method of the modified starch in the embodiment of the invention comprises the following steps:
firstly, uniformly mixing 2 parts by weight of starch and 100 parts by weight of water at 90 ℃, then adding 5 parts by weight of ferric acetate, and reacting for 2 hours at normal temperature (about 25 ℃), thus obtaining the modified starch.
Example 1 of the present invention is: starch-based elastomer and preparation method thereof:
the starch-based elastomer comprises the following preparation raw materials: 40 parts of polypropylene carbonate polyol (Jiangsu golden dragon JLB-B2350); 10 parts of polycaprolactone diol (basf PCL 1000); 10 parts of modified starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 parts of a catalyst (stannous octoate); 3 parts of an antioxidant (Basoff, antioxidant 1010, CAS number 6683-19-8); 5 parts of chain extender (isophorone diisocyanate, bayer, CAS number: 4098-71-9) and 1 part of plasticizer (glycerol).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting modified starch and straw into a high-speed mixer, stirring for 10min at the rotating speed of 300rpm/min, and uniformly mixing the modified starch and the straw to form a premix;
s2, sequentially adding the premix, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer prepared in the step S1 into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, stirring the materials uniformly at the rotating speed of 1000rpm/min for 30min to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, melting, extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw speed is 400rpm/min, the vacuum degree is 0.05MPa.
Example 2 of the present invention is: starch-based elastomer and preparation method thereof:
the starch-based elastomer comprises the following preparation raw materials: 50 parts of polypropylene carbonate polyol (Jiangsu golden dragon JLB-H2200); 25 parts of polycaprolactone diol (basf PCL 1000); 25 parts of modified starch; 40 parts of straw; 5 parts of filler (carboxylated nano titanium dioxide); 1 part of catalyst (stannous octoate); 5 parts of an antioxidant (basf Tinuvin B75 ED); 10 parts of chain extender (Basoff T-80) and 3 parts of plasticizer (urea).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting modified starch and straw into a high-speed mixer, stirring for 5-10 min at the rotating speed of 300rpm/min, and uniformly mixing the modified starch and the straw to form a premix;
s2, sequentially adding the premix, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer prepared in the step S1 into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer at a rotating speed of 1000rpm/min for 20-30 min, and uniformly stirring the materials to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, melting, extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 120-180 ℃, the screw speed is 400rpm/min, the vacuum degree is 0.04-0.05 MPa.
Example 3 of the present invention is: starch-based elastomer and preparation method thereof:
the starch-based elastomer comprises the following preparation raw materials: 45 parts of polypropylene carbonate polyol (Jiangsu golden dragon JLB-B2350); 15 parts of polycaprolactone diol (basf PCL 1000); 15 parts of modified starch; 30 parts of straw; filler (carboxylated nano titanium dioxide 3 parts, aminated nano zinc oxide 2 parts); 0.81 parts of catalyst (stannous octoate); antioxidants (Basoff, antioxidant 1010, CAS number 6683-19-8); 8 parts of chain extender (Wanhua MDI-50) and 1 part of plasticizer (formamide).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting modified starch and straw into a high-speed mixer, stirring for 5-10 min at the rotating speed of 300rpm/min, and uniformly mixing the modified starch and the straw to form a premix;
s2, sequentially adding the premix, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer prepared in the step S1 into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer at a rotating speed of 1000rpm/min for 20-30 min, and uniformly stirring the materials to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, melting, extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 120-180 ℃, the screw speed is 400rpm/min, the vacuum degree is 0.04-0.05 MPa.
Example 4 of the present invention is: starch-based elastomer and preparation method thereof:
the starch-based elastomer comprises the following preparation raw materials: 50 parts of polypropylene carbonate polyol (Jiangsu golden dragon JLB-H2200); 20 parts of polycaprolactone diol (basf PCL 1000); 15 parts of modified starch; 30 parts of straw; 4 parts of filler (zinc oxide); 1 part of catalyst (stannous octoate); 3 parts of an antioxidant (Basoff, antioxidant 1010, CAS number 6683-19-8); 5 parts of chain extender (Basoff T-80) and 3 parts of plasticizer (urea).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting modified starch and straw into a high-speed mixer, stirring for 5-10 min at the rotating speed of 300rpm/min, and uniformly mixing the modified starch and the straw to form a premix;
s2, sequentially adding the premix, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer prepared in the step S1 into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer at a rotating speed of 1000rpm/min for 20-30 min, and uniformly stirring the materials to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, melting, extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 120-180 ℃, the screw speed is 400rpm/min, the vacuum degree is 0.04-0.05 MPa.
Example 5 of the present invention is: starch-based elastomer and preparation method thereof:
the starch-based elastomer comprises the following preparation raw materials: 45 parts of polypropylene carbonate polyol (Jiangsu golden dragon JLB-B2350); 25 parts of polycaprolactone diol (basf PCL 1000); 15 parts of modified starch; 30 parts of straw; 5 parts of filler (aminated nano zinc oxide); catalysts (stannous octoate); 3 parts of an antioxidant (Basoff, antioxidant 1010, CAS number 6683-19-8); 1 part of chain extender (Basoff T-80) 5 parts and 3 parts of plasticizer (urea).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting modified starch and straw into a high-speed mixer, stirring for 5-10 min at the rotating speed of 300rpm/min, and uniformly mixing the modified starch and the straw to form a premix;
s2, sequentially adding the premix, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer prepared in the step S1 into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer at a rotating speed of 1000rpm/min for 20-30 min, and uniformly stirring the materials to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, melting, extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 120-180 ℃, the screw speed is 400rpm/min, the vacuum degree is 0.04-0.05 MPa.
Comparative example 1 of the present invention is: starch-based elastomer and preparation method thereof:
the starch-based elastomer comprises the following preparation raw materials: 40 parts of polypropylene carbonate polyol (Jiangsu golden dragon JLB-B2350); 10 parts of polycaprolactone diol (basf PCL 1000); 10 parts of starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 parts of a catalyst (stannous octoate); 3 parts of an antioxidant (Basoff, antioxidant 1010, CAS number 6683-19-8); 5 parts of chain extender (isophorone diisocyanate, bayer, CAS number: 4098-71-9) and 1 part of plasticizer (glycerol).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting starch and straw into a high-speed mixer, stirring for 10min at the rotating speed of 300rpm/min, and uniformly mixing the modified starch and the straw to form a premix;
s2, sequentially adding the premix, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer prepared in the step S1 into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, stirring the materials uniformly at the rotating speed of 1000rpm/min for 30min to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, melting, extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw speed is 400rpm/min, the vacuum degree is 0.05MPa.
Comparative example 2 of the present invention is: starch-based elastomer and preparation method thereof:
the starch-based elastomer comprises the following preparation raw materials: 40 parts of polypropylene carbonate polyol (Jiangsu golden dragon JLB-B2350); 10 parts of polycaprolactone diol (basf PCL 1000); 10 parts of modified starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 parts of a catalyst (stannous octoate); 3 parts of an antioxidant (Basoff, antioxidant 1010, CAS number: 6683-19-8) and 5 parts of a chain extender (isophorone diisocyanate, bayer, CAS number: 4098-71-9).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting modified starch and straw into a high-speed mixer, stirring for 10min at the rotating speed of 300rpm/min, and uniformly mixing the modified starch and the straw to form a premix;
s2, sequentially adding the premix, the filler, the catalyst, the antioxidant and the chain extender prepared in the step S1 into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, stirring the materials uniformly for 30min at the rotating speed of 1000rpm/min, and obtaining a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, melting, extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw speed is 400rpm/min, the vacuum degree is 0.05MPa.
Comparative example 3 of the present invention is: starch-based elastomer and preparation method thereof:
the starch-based elastomer comprises the following preparation raw materials: 40 parts of polypropylene carbonate polyol (Jiangsu golden dragon JLB-B2350); 10 parts of modified starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 parts of a catalyst (stannous octoate); 3 parts of an antioxidant (Basoff, antioxidant 1010, CAS number 6683-19-8); 5 parts of chain extender (isophorone diisocyanate, bayer, CAS number: 4098-71-9) and 1 part of plasticizer (glycerol).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting modified starch and straw into a high-speed mixer, stirring for 10min at the rotating speed of 300rpm/min, and uniformly mixing the modified starch and the straw to form a premix;
s2, sequentially adding the premix, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer prepared in the step S1 into a high-speed mixer, then adding the polypropylene carbonate polyol into the high-speed mixer, stirring the materials uniformly for 30min at the rotating speed of 1000rpm/min to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, melting, extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw speed is 400rpm/min, the vacuum degree is 0.05MPa.
Comparative example 4 of the present invention is: starch-based elastomer and preparation method thereof:
the starch-based elastomer comprises the following preparation raw materials: 10 parts of polycaprolactone diol (basf PCL 1000); 10 parts of modified starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 parts of a catalyst (stannous octoate); 3 parts of an antioxidant (Basoff, antioxidant 1010, CAS number 6683-19-8); 5 parts of chain extender (isophorone diisocyanate, bayer, CAS number: 4098-71-9) and 1 part of plasticizer (glycerol).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting modified starch and straw into a high-speed mixer, stirring for 10min at the rotating speed of 300rpm/min, and uniformly mixing the modified starch and the straw to form a premix;
s2, sequentially adding the premix, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer prepared in the step S1 into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, stirring the materials uniformly at the rotating speed of 1000rpm/min for 30min to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, melting, extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw speed is 400rpm/min, the vacuum degree is 0.05MPa.
Performance test:
(1) Biodegradation test: the starch-based elastomer films prepared in examples and comparative examples of the present invention were obtained by extrusion casting, and the starch-based elastomer films prepared in examples 1 to 5 and comparative examples 1 to 4 were subjected to a soil-burying decomposition test according to GB/T17303-2017, and 10.0g of the films were buried under the ground, and the appearance and weight loss of the films were measured after three months.
(2) Physical and mechanical performance test: the mechanical properties are referred to GB/T1040-1979, and the stretching rate is 200mm/min.
TABLE 1 results of Performance test of starch-based elastomer prepared in examples one to five and comparative examples one to five
As can be seen from the data in Table 1, the starch-based elastomers prepared in examples 1 to 5 of the present invention have a better degradation ability than the starch-based elastomers prepared in comparative examples one to five, and the abrasion resistance of the starch-based elastomers prepared in the present invention is significantly improved.
Compared with the example 1, the modified starch is replaced by the common starch, the biodegradation degree of the prepared elastomer is 27.4 percent, which is far lower than 89.3 percent in the example 1, and the mechanical property is poor.
In comparative example 2, the workability of starch was inferior to that of example 1 without adding a plasticizer, so that the mechanical properties of the elastomer were lowered.
Compared with the example 1, the comparative example 3 of the invention does not add polycaprolactone diol, the biodegradation degree of the prepared elastomer is 47.2 percent, which is far lower than 89.3 percent of the biodegradation degree in the example 1, and the mechanical property is poor.
Compared with the example 1, the comparative example 4 of the invention does not add the polypropylene carbonate polyol, the biodegradation degree of the prepared elastomer is 50.2 percent, which is far lower than 89.3 percent in the example 1, and the mechanical property is poor.
As can be seen from comparative examples 1 to 4, the invention utilizes the synergistic effect of the polypropylene carbonate polyol, the polycaprolactone diol and the modified starch, not only ensures that the starch-based elastomer has good microbial degradability, but also maintains good mechanical properties; after the starch-based elastomer is degraded for 90 days, the mass loss reaches 86.5%, and the elongation at break reaches more than 830%.
In conclusion, the complex is formed by ferric ions and starch, the coordination clusters formed by coordination reaction have physical crosslinking effect, can limit the movement of starch molecular chains, improve the shearing viscosity of melt, play a role in reverse plasticization, increase the extrusion residence time of melt, further improve the shearing degradation effect of the screw rod to a certain extent, and improve the strength and the thermal stability of starch. The elastomer prepared by the modified starch has good mechanical property and degradability.
While the embodiments of the present invention have been described in detail in connection with the description, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of one of ordinary skill in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (16)
1. A starch-based elastomer characterized in that: the material comprises the following raw materials in parts by weight:
40-50 parts of polypropylene carbonate polyol;
10-25 parts of polycaprolactone diol;
10-25 parts of modified starch;
20-40 parts of straw;
1-5 parts of filler;
0.5-1 part of catalyst;
3-5 parts of antioxidant;
5-10 parts of chain extender;
1-3 parts of plasticizer;
the modified starch is iron ion modified starch.
2. A starch-based elastomer according to claim 1, characterized in that: the molecular weight of the polypropylene carbonate polyol is 2000-5000.
3. A starch-based elastomer according to claim 1, characterized in that: the molecular weight of the polycaprolactone diol is 1000-4000.
4. A starch-based elastomer according to claim 1, characterized in that: the preparation raw materials of the iron ion modified starch comprise starch and ferric salt.
5. A starch-based elastomer according to claim 1, characterized in that: the iron ion modified starch comprises the following preparation raw materials in parts by weight: 1 part of starch and 2-3 parts of ferric salt.
6. A starch-based elastomer according to claim 5, wherein: the preparation method of the iron ion modified starch comprises the following steps: preparing a starch solution, and adding the ferric salt into the starch solution for reaction.
7. A starch-based elastomer according to claim 1, characterized in that: the filler comprises a nanofiller.
8. A starch-based elastomer according to claim 7, wherein: the nanofiller includes at least one of nano titanium dioxide and nano zinc oxide.
9. A starch-based elastomer according to claim 8, wherein: the nano-titania includes modified nano-titania.
10. A starch-based elastomer according to claim 8, wherein: the nano zinc oxide includes modified nano zinc oxide.
11. A starch-based elastomer according to claim 1, characterized in that: the chain extender comprises at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
12. A starch-based elastomer according to claim 1, characterized in that: the catalyst comprises at least one of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, tin dioctanoate and dibutyl tin dilaurate.
13. A starch-based elastomer according to claim 1, characterized in that: the antioxidant comprises one of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants, sulfur-containing synergists and benzofuranone derivatives.
14. A starch-based elastomer according to claim 1, characterized in that: the plasticizer includes at least one of formamide, glycerin, and urea.
15. A process for preparing a starch-based elastomer according to any one of claims 1 to 14, characterized in that: the method comprises the following steps:
s1, mixing modified starch and straw to form a premix;
s2, mixing the premix prepared in the step S1, the filler and the auxiliary agent, adding polycaprolactone diol and polypropylene carbonate polyol, and mixing again to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, and extruding and granulating to obtain the starch-based elastomer.
16. Use of a starch-based elastomer according to any one of claims 1 to 14 for the preparation of a degradable material.
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