CN110577673B - A kind of hydrophobic thermoplastic starch modified by polyionic liquid and preparation method thereof - Google Patents
A kind of hydrophobic thermoplastic starch modified by polyionic liquid and preparation method thereof Download PDFInfo
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- 229920008262 Thermoplastic starch Polymers 0.000 title claims abstract description 61
- 239000004628 starch-based polymer Substances 0.000 title claims abstract description 58
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 54
- 239000007788 liquid Substances 0.000 title claims abstract description 53
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920002261 Corn starch Polymers 0.000 claims abstract description 23
- 239000008120 corn starch Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000012265 solid product Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229940099112 cornstarch Drugs 0.000 claims 3
- 229920002472 Starch Polymers 0.000 abstract description 28
- 235000019698 starch Nutrition 0.000 abstract description 28
- 239000008107 starch Substances 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 20
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 6
- 229920001169 thermoplastic Polymers 0.000 abstract description 6
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 6
- 239000004014 plasticizer Substances 0.000 description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 dodecylbenzene sulfonate ion Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
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- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
本发明公开了一种聚离子液体改性的疏水型热塑性淀粉及其制备方法。所述热塑性淀粉包括玉米淀粉及聚离子液体。制备方法为：将玉米淀粉和聚离子液体分别溶于二甲基亚砜中，然后混合，加热并搅拌；将混合物烘干除去二甲基亚砜，得到固体产物；对固体产物加热熔融后压制成膜，得到热塑性淀粉膜。Poly[ECH‑MIM]‑DBS可与玉米淀粉形成新的氢键作用，使得淀粉处于无定形状态而具有热塑性。此外，原先亲水的玉米淀粉在聚离子液体Poly[ECH‑MIM]‑DBS的增塑下表现为疏水性，这一定程度上可以减少由于亲水对热塑性淀粉材料性能的影响，拓展了热塑性淀粉材料的应用。
The invention discloses a hydrophobic thermoplastic starch modified by polyionic liquid and a preparation method thereof. The thermoplastic starch includes corn starch and polyionic liquid. The preparation method is as follows: dissolving corn starch and polyionic liquid in dimethyl sulfoxide respectively, then mixing, heating and stirring; drying the mixture to remove dimethyl sulfoxide to obtain a solid product; heating and melting the solid product and then pressing A film is formed to obtain a thermoplastic starch film. Poly[ECH‑MIM]‑DBS can form new hydrogen bonds with corn starch, making the starch in an amorphous state and thermoplastic. In addition, the originally hydrophilic corn starch showed hydrophobicity under the plasticization of the polyionic liquid Poly[ECH‑MIM]‑DBS, which could reduce the influence of hydrophilicity on the properties of thermoplastic starch materials to a certain extent, and expanded the thermoplastic starch. material application.
Description
Technical Field
The invention belongs to the field of starch deep processing, and particularly relates to hydrophobic thermoplastic starch prepared by using polyion liquid as a macromolecular plasticizer and a preparation method thereof.
Background
The melting temperature of the starch is higher than the decomposition temperature due to the strong hydrogen bond interaction among molecules in the starch molecule, namely the starch cannot be subjected to thermoplastic processing, so that the application of the starch is greatly limited, and the advantage of biodegradability of the starch cannot be fully exerted, so that the research of the thermoplasticity of the starch by utilizing the plasticizer draws the attention of researchers. Common plasticizers include glycerin, urea, sorbitol and other small molecules, which can effectively form hydrogen bond with starch molecules and lubricate during thermal processing, so that the starch molecules can perform chain motion at a lower temperature and show thermoplasticity macroscopically. However, this plasticizing system has the problem that small molecules are easy to migrate, and after the plasticized thermoplastic starch is stored for a period of time, aggregation and overflow of the plasticizer can be observed by means of an environmental Scanning Electron Microscope (SEM), which can affect the performance stability of the thermoplastic starch material and even cause it to lose its thermoplasticity. Therefore, effectively keeping the properties of the thermoplastic starch material stable is another difficulty which is continuously solved in starch thermoplasticity. In recent years, research shows that Ionic Liquid (IL) has good dissociation effect on a strong hydrogen bond network as a novel solvent, so more and more researchers introduce the ionic liquid into the development of thermoplastic starch. It was found that ionic liquids can impart better hydrophobicity to thermoplastic starch materials and have higher plasticization efficiency than the glycerol system thermoplastic starch materials, but ionic liquids are also a disadvantage of the presence of small molecule plasticizers.
Compared with a micromolecule plasticizer, the macromolecule plasticizer can be stabilized in a plasticized system due to molecular chain entanglement and the like, and the problem caused by plasticizer migration can be solved. However, the newly reported article using polyester-based plasticizers shows that the compatibility between macromolecular plasticizers and starch directly affects the plasticizing effect and the performance of thermoplastic starch materials. Therefore, if a macromolecular plasticizer which can successfully solve the problems of easy migration of small molecules and compatibility with starch can be designed and synthesized, the method has important significance for preparing the thermoplastic starch material with stable performance.
Moreover, the polyhydroxy structure of the starch has certain hydrophilicity, so that the requirement on the environment is relatively high in the application process, and certain limitation is realized, so that if the thermoplastic starch material can be further endowed with hydrophobicity, the application problem can be effectively solved, and the application of the starch is expanded.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a polyion liquid modified hydrophobic thermoplastic starch and a preparation method thereof.
In order to solve the problems, the invention provides polyion liquid modified hydrophobic thermoplastic starch, which is characterized by comprising corn starch and polyion liquid, wherein the mass ratio of the corn starch to the polyion liquid is (1.0-9.0): 1, wherein the polyionic liquid is Poly [ ECH-MIM ] -DBS.
Preferably, the chemical structural formula of the polyion liquid is as follows:
wherein n is 50-5000.
3. The method for preparing polyion liquid modified hydrophobic thermoplastic starch as claimed in claim 1 or 2, characterized by comprising the steps of:
step 1): respectively dissolving corn starch and polyion liquid in dimethyl sulfoxide (DMSO), mixing, heating and stirring;
step 2): drying the mixture obtained in the step 1) to remove dimethyl sulfoxide to obtain a solid product;
step 3): heating and melting the solid product obtained in the step 2), and pressing the solid product into a film to obtain the thermoplastic starch film.
Preferably, the concentration of the corn starch dissolved in the dimethyl sulfoxide in the step 1) is 0.08-0.2 g/mL; the concentration of the polyion liquid is 0-0.12g/mL after the polyion liquid is dissolved in dimethyl sulfoxide.
Preferably, the heating temperature in the step 1) is 60-110 ℃, the mechanical stirring speed is 150-300r/min, and the heating and stirring time is 50-90 min.
Preferably, the drying temperature in the step 2) is 70-90 ℃, and the drying time is 48-72 h.
Preferably, in the step 3), a flat vulcanizing press is adopted to heat and melt the solid product and pressurize the solid product to form a film, and thenThe heating temperature is 150-2The pressurizing time is 15-45 s.
The principle of the invention is that firstly imidazole and epichlorohydrin are used as monomers, and Poly [ ECH-MIM ] -DBS with dodecylbenzene sulfonate ion as anion is synthesized through quaternization reaction and ion exchange reaction; the starch is used as a plasticizer to be mixed with starch, and new hydrogen bonding effect is generated by utilizing anions and cations of the polyionic liquid and hydroxyl groups on starch molecular chains, so that the hydrogen bonding effect between the molecular chains is greatly weakened compared with that of the original starch, the starch molecular chains can slide at a relatively low temperature, and the melting phenomenon is macroscopically expressed, thus obtaining the thermoplastic starch. On the other hand, due to the hydrophobicity of the polyion liquid Poly [ ECH-MIM ] -DBS anion, the thermoplastic starch material can be endowed with hydrophobicity, and the hydrophobic thermoplastic starch in the invention has hydrophobicity after secondary thermoplastic processing, which is different from the common surface hydrophobic modification. The thermoplastic starch material plasticized by the polyionic liquid can be pressed into a sheet by a flat vulcanizing machine, which fully represents the thermoplasticity of the material. And the infrared spectrum, the differential scanning calorimetry image, the thermal weight loss image and the mechanical property test can be used as effective means for analyzing the interaction of the corn starch and the polyion liquid. Particularly, the contact angle of the material is tested by using a full-automatic video microcosmic contact angle measuring instrument, so that the hydrophilicity and hydrophobicity of the material are judged.
The polyionic liquid Poly [ ECH-MIM ] -DBS is designed and synthesized and is used for preparing hydrophobic thermoplastic starch, an imidazole cationic ionic liquid unit is contained on the main chain of the polyionic liquid, and the polyionic liquid contains a hydroxyl structure, anions and cations can form hydrogen bond action with hydroxyl of a starch molecular chain, the effect of effectively avoiding the recombination of the hydrogen bond of starch molecules is achieved, the starch is in an amorphous state, so that the starch obtains thermoplastic processing performance, and hydrophobic dodecyl benzene sulfonate ions on the Poly [ ECH-MIM ] -DBS can bring hydrophobicity to the thermoplastic starch; the preparation method is simple, does not use micromolecular plasticizers, is different from common surface hydrophobic modification, and the obtained thermoplastic starch still has hydrophobicity after secondary thermoplastic processing and good mechanical property, thereby expanding the application field of the starch, optimizing the performance of the thermoplastic starch material and developing the application value of the starch more greatly.
Compared with the prior art, the invention has the beneficial effects that:
the invention utilizes polyion liquid Poly [ ECH-MIM ] -DBS as a macromolecule plasticizer to prepare thermoplastic starch, and modifies the thermoplastic starch to ensure that the starch material has hydrophobicity, and compared with the common surface hydrophobic modified material, the starch material still has hydrophobicity after secondary thermoplastic processing; compared with thermoplastic starch prepared by micromolecular plasticizers, the thermoplastic starch prepared by the method has the advantages of no problem of easy migration of the plasticizer, simple preparation and high mechanical property.
Drawings
FIG. 1 is an infrared spectrum of Poly [ ECH-MIM ] -DBS as the polyion liquid in the invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of Poly [ ECH-MIM ] -DBS in the present invention;
FIG. 3 is an infrared spectrum of hydrophobic thermoplastic starch prepared in examples 1 to 3 and a comparative example;
FIG. 4 is a differential scanning calorimetry trace of hydrophobic thermoplastic starches obtained in examples 1 to 3 and comparative example;
FIG. 5 is a photograph of a sheet prepared by a press vulcanizer comprising corn starch and the hydrophobic thermoplastic starch obtained in example 1;
FIG. 6 is a contact angle image of hydrophobic thermoplastic starches obtained in examples 1 to 3 and comparative example.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Macromolecular plasticizer polyionic liquid Poly [ ECH-MIM ] in examples 1-3]-DBSs are each of the structural formula:
n＝1200。
the preparation process of the polyion liquid Poly [ ECH-MIM ] -DBS comprises the following steps: preparing imidazole into 1mol/L aqueous solution, placing the aqueous solution in a reactor, cooling to-5 ℃, and slowly dropwise adding epichlorohydrin with the same molar quantity as the imidazole under stirring; after the dropwise addition is finished, stirring is continued for 12 hours; then heating to 95 ℃, and stirring for reaction for 7 days; and then stopping the reaction, after the reaction liquid is cooled to room temperature, pouring the reaction liquid into acetone with the volume of 20 times, collecting the obtained precipitate, putting the precipitate into a vacuum oven, drying the precipitate for 24 hours at 80 ℃ to obtain light yellow solid, preparing the solid product into 1mol/L aqueous solution, pouring the aqueous solution of sodium dodecyl benzene sulfonate with the same molar concentration, standing the solution for 24 hours, collecting the obtained white precipitate, putting the white precipitate into the vacuum oven, and drying the white precipitate for 24 hours at 80 ℃ to obtain off-white solid, namely the target product polyion liquid Poly [ ECH-MIM ] -DBS.
The thermoplastic starches obtained in the examples and in the control were subjected to plasticizer mobility tests with reference to the standard ISO 177. The test principle is as follows: the test specimen is placed between and in intimate contact with two plasticizer-absorbing sheets, heated under specified conditions, and the mass loss of the specimen is measured to characterize plasticizer migration as follows: the plasticizer-absorbing material is polyvinyl alcohol without plasticizer, a sample to be tested with thickness of 1mm and 5cm × 5cm is placed between two absorption sheets during measurement, the axes are aligned to form a sandwich structure, the sample is placed in an environment with constant temperature of 70 ℃ under the pressure of 5kg, and after 24h, the sample is taken out and treated to measure the mass loss of the sample.
And (3) determination of melt index: using a melt index apparatus, the capillary diameter was 2.095mm and the tube length was 8 mm. After heating to 190 ℃, the upper end was pressed downward with a 2.16kg weight applied by a piston, and the weight of the sample extruded in 10 minutes was measured as the melt index of the sample.
Example 1
A polyion liquid modified hydrophobic thermoplastic starch has a hot processing temperature of 180 ℃, a tensile strength of 9.47MPa, an elongation at break of 3.14%, a contact angle of 117.3 degrees, a plasticizer mobility of 1.52% and a melt index of 7.2g/10 min.
The preparation method of the polyion liquid modified hydrophobic thermoplastic starch comprises the following steps:
step a: weighing 9g and 1g of corn starch and polyion liquid Poly [ ECH-MIM ] -DBS respectively for later use;
step b: dissolving 9g of corn starch in 50mL of dimethyl sulfoxide (DMSO), dissolving 1g of polyion liquid in 50mL of DMSO, and uniformly mixing the two solutions for later use;
step c: b, uniformly stirring the mixed solution in the step b at the rotation speed of 200r/min at the temperature of 90 ℃, and timing for 60 min;
step d: drying the mixture obtained in the step c at 80 ℃ for 72h to remove dimethyl sulfoxide to obtain a solid product;
step e: and d, setting the heating temperature of the flat vulcanizing machine to be 180 ℃ and the pressure to be 50kg/cm2, heating and melting the solid product obtained in the step d for 5min, pressurizing for 30s, and cooling to obtain the thermoplastic starch sheet.
Example 2
A polyion liquid modified hydrophobic thermoplastic starch has a hot processing temperature of 160 ℃, a tensile strength of 7.68MPa, an elongation at break of 4.27%, a contact angle of 117.1 degrees, a plasticizer mobility of 1.96%, and a melt index of 7.5g/10 min.
The preparation method of the polyion liquid modified hydrophobic thermoplastic starch comprises the following steps:
step a: weighing corn starch and polyion liquid Poly [ ECH-MIM ] -DBS (PolyEthyl methacrylate-Polytetrafluoroethylene) which are 7g and 3g respectively for later use;
step b: dissolving 7g of corn starch in 50mL of dimethyl sulfoxide (DMSO), dissolving 3g of polyion liquid in 50mL of DMSO, and uniformly mixing the two solutions for later use;
step c: b, uniformly stirring the mixed solution in the step b at the rotating speed of 250r/min at the temperature of 80 ℃, and timing for 50 min;
step d: drying the mixture obtained in the step c at 70 ℃ for 72h to remove dimethyl sulfoxide to obtain a solid product;
step e: and d, setting the heating temperature of the plate vulcanizing machine to be 160 ℃ and the pressure to be 50kg/cm2, heating and melting the solid product obtained in the step d for 3min, pressurizing for 30s, and cooling to obtain the thermoplastic starch sheet.
Example 3
A polyion liquid modified hydrophobic thermoplastic starch has a hot processing temperature of 150 ℃, a tensile strength of 7.04MPa, an elongation at break of 4.76%, a contact angle of 114.7 degrees, a plasticizer mobility of 2.33%, and a melt index of 8.1g/10 min.
The preparation method of the polyion liquid modified hydrophobic thermoplastic starch comprises the following steps:
step a: weighing corn starch and polyion liquid Poly [ ECH-MIM ] -DBS, wherein the weight is 4g and 6g respectively for later use;
step b: dissolving 4g of corn starch in 50mL of dimethyl sulfoxide (DMSO), dissolving 6g of polyion liquid in 50mL of DMSO, and uniformly mixing the two solutions for later use;
step c: b, uniformly stirring the mixed solution in the step b at the rotating speed of 300r/min at the temperature of 70 ℃, and timing for 50 min;
step d: drying the mixture obtained in the step c at 70 ℃ for 72h to remove dimethyl sulfoxide to obtain a solid product;
step e: and d, setting the heating temperature of the flat vulcanizing machine to be 150 ℃ and the pressure to be 30kg/cm2, heating and melting the solid product obtained in the step d for 2min, pressurizing for 15s, and cooling to obtain the thermoplastic starch sheet.
Comparative example
A glycerol plasticized thermoplastic starch material having a hot working temperature of 165 ℃, a tensile strength of 4.73MPa, an elongation at break of 5.75%, a contact angle of 78.7 °, a plasticizer mobility of 29.64%, and a melt index of 6.5g/10 min.
The preparation method of the glycerin plasticized thermoplastic starch material comprises the following steps:
step a: weighing corn starch and glycerol respectively in an amount of 7g and 2g for later use;
step b: dissolving 7g of corn starch in 100mL of deionized water, adding 2g of glycerol, and uniformly mixing for later use;
step c: uniformly stirring the mixed solution in the step b at the rotation speed of 150r/min at the temperature of 90 ℃, and timing for 90 min;
step d: c, drying the mixture obtained in the step c at 90 ℃ for 48 hours to remove water, and obtaining a solid product;
step e: and d, setting the heating temperature of the plate vulcanizing machine to be 165 ℃ and the pressure to be 30kg/cm2, heating and melting the solid product obtained in the step d for 3min, pressurizing for 15s, and cooling to obtain the thermoplastic starch sheet.
FIG. 5 is a photograph of a sheet obtained by hot-pressing corn starch and the hydrophobic thermoplastic starch obtained in example 1, and compared with a corn starch sample, the sheet of this example has good transparency and regular shape, which shows that the polyion liquid modified hydrophobic thermoplastic starch obtained in example has good thermoplasticity.
FIG. 6 is a contact angle image of thermoplastic starch obtained in comparative example 1, which has a contact angle of 78.7 degrees and is shown to be hydrophilic, and in examples 1, 2 and 3, which has contact angles of 117.3 degrees, 117.1 degrees and 114.7 degrees, respectively, which are larger than 90 degrees and are shown to be hydrophobic, and examples 1, 2 and 3, which illustrate that hydrophobic thermoplastic starch can be obtained after modification by polyionic liquid Poly [ ECH-MIM ] -DBS.
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| CN1816592A (en) * | 2003-07-08 | 2006-08-09 | 罗盖特公司 | Cationic liquid starchy composition and uses thereof |
| JP2007530743A (en) * | 2004-03-26 | 2007-11-01 | ザ ユニヴァーシティー オブ アラバマ | Polymer dissolution and blend formation in ionic liquids |
| CN105418977A (en) * | 2015-11-11 | 2016-03-23 | 华南理工大学 | Starch-based conductive composite film built on basis of ionic liquid enhanced starch phase change, method and application |
| CN109333953A (en) * | 2018-09-25 | 2019-02-15 | 太仓欧典新材料有限公司 | A kind of preparation method of modified starch/PBS intermingling material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1816592A (en) * | 2003-07-08 | 2006-08-09 | 罗盖特公司 | Cationic liquid starchy composition and uses thereof |
| JP2007530743A (en) * | 2004-03-26 | 2007-11-01 | ザ ユニヴァーシティー オブ アラバマ | Polymer dissolution and blend formation in ionic liquids |
| CN105418977A (en) * | 2015-11-11 | 2016-03-23 | 华南理工大学 | Starch-based conductive composite film built on basis of ionic liquid enhanced starch phase change, method and application |
| CN109333953A (en) * | 2018-09-25 | 2019-02-15 | 太仓欧典新材料有限公司 | A kind of preparation method of modified starch/PBS intermingling material |
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