CN116082715A - High heat-resistant thermoplastic starch and preparation method thereof - Google Patents
High heat-resistant thermoplastic starch and preparation method thereof Download PDFInfo
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- CN116082715A CN116082715A CN202310064155.0A CN202310064155A CN116082715A CN 116082715 A CN116082715 A CN 116082715A CN 202310064155 A CN202310064155 A CN 202310064155A CN 116082715 A CN116082715 A CN 116082715A
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- 229920008262 Thermoplastic starch Polymers 0.000 title claims abstract description 56
- 239000004628 starch-based polymer Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000004014 plasticizer Substances 0.000 claims abstract description 19
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 229920002472 Starch Polymers 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 235000019698 starch Nutrition 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 239000008107 starch Substances 0.000 claims abstract description 17
- 239000004611 light stabiliser Substances 0.000 claims abstract description 16
- FFYTTYVSDVWNMY-UHFFFAOYSA-N 2-Methyl-5-nitroimidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1 FFYTTYVSDVWNMY-UHFFFAOYSA-N 0.000 claims abstract description 14
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000003351 stiffener Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- WOKDXPHSIQRTJF-UHFFFAOYSA-N 3-[3-[3-[3-[3-[3-[3-[3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)CO WOKDXPHSIQRTJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 9
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000011265 semifinished product Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000019359 magnesium stearate Nutrition 0.000 claims description 4
- 229920001046 Nanocellulose Polymers 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 2
- 229920000856 Amylose Polymers 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000012748 slip agent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 241000276425 Xiphophorus maculatus Species 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract 2
- 235000011187 glycerol Nutrition 0.000 description 11
- 229920002261 Corn starch Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008120 corn starch Substances 0.000 description 8
- 229940105990 diglycerin Drugs 0.000 description 8
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000007792 addition Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 whisker Substances 0.000 description 1
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K3/34—Silicon-containing compounds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses high heat-resistant thermoplastic starch, which comprises 100 parts by weight of main material and 5-12.8 parts by weight of auxiliary material, wherein the main material comprises starch and plasticizer, and the plasticizer comprises glycerol, diglycerol and decaglycerol; the auxiliary materials comprise 2-methyl-5-nitroimidazole, a stiffening agent, a chain extender, a stabilizer, an antioxidant, a light stabilizer, a slipping agent and a surfactant. The invention improves the thermal deformation temperature of the thermoplastic starch to above 82 ℃, and effectively improves the bending strength and the bending modulus of the thermoplastic starch.
Description
Technical Field
The invention relates to the field of materials, in particular to high heat-resistant thermoplastic starch and a preparation method thereof.
Background
Thermoplastic starch (TPS) is an amorphous compound prepared from starch and a plasticizer by a certain means, has lower cost and excellent biocompatibility, is particularly suitable for preparing a full-biodegradable composite material after being compounded with biodegradable plastics, and is compared with the biodegradable plastics: obvious cost advantage, good regenerability and low carbon emission of raw materials.
However, thermoplastic starch is an amorphous structure compound whose rheological properties determine its tendency to soften after heating, a significant decrease in strength, particularly a low heat distortion temperature, which limits the use of thermoplastic starch as a filler in fully biodegradable cutlery materials.
Therefore, the method is used for changing the rheological property of the thermoplastic starch, improving the thermal deformation temperature of the thermoplastic starch, and being beneficial to expanding the use scene of the thermoplastic starch, so that the thermoplastic starch can be used in a large amount in disposable tableware and other materials, and the aim of reducing the cost of the fully biodegradable tableware material is fulfilled.
Improving the heat resistance of thermoplastic starch by utilizing the supermolecular coordination of hydroxyl groups in starch and other compounds is a novel means. Patent CN110498950a discloses a thermoplastic starch based on coordination effect, a preparation method and application thereof, wherein anhydrous zinc acetate is doped into the thermoplastic starch, and the glass transition temperature of the thermoplastic starch can be improved by utilizing the coordination effect of the anhydrous zinc acetate.
The heat resistance of the thermoplastic starch resin is improved by adding 15-30 parts of natural fibers in the patent CN 112457534A.
Patent CN111763354a utilizes modified octaphenyl-POSS to modify thermoplastic starch, so that it has better heat resistance.
However, although the heat resistance of the thermoplastic starch is improved to a certain extent, the performance of the thermoplastic starch is still insufficient at present to enable the thermoplastic starch to meet the strength and heat distortion temperature requirements, and the heat distortion temperature of the composite material product is still low
Disclosure of Invention
In order to solve the technical problems, the invention provides high heat-resistant thermoplastic starch and a preparation method thereof.
The aim of the invention is achieved by the following technical scheme:
a high heat-resistant thermoplastic starch comprises 100 parts by weight of main materials and 5-12.8 parts by weight of auxiliary materials, wherein the main materials comprise starch and a plasticizer, and the plasticizer comprises glycerol, diglycerol and decaglycerol; the auxiliary materials comprise 2-methyl-5-nitroimidazole, a stiffening agent, a chain extender, a stabilizer, an antioxidant, a light stabilizer, a slipping agent and a surfactant;
the mass ratio range of each raw material in the main material is as follows:
75-80% of starch, 10-16% of glycerol, 2-5% of diglycerol and 2-5% of decaglycerol;
the main materials are used as the reference, and the mass ratio ranges of the raw materials of the auxiliary materials are as follows: comprises 1 to 3 weight parts of 2-methyl-5-nitroimidazole, 2 to 5 weight parts of stiffening agent, 0.1 to 0.3 weight part of chain extender, 0.3 to 0.5 weight part of stabilizer, 0.5 to 1.5 weight parts of antioxidant, 0.1 to 0.5 weight part of light stabilizer, 0.5 to 1 weight part of slipping agent and 0.5 to 1 weight part of surfactant.
Further improved, the stiffening agent is one of nanocellulose, light calcium carbonate and flaky mica powder.
Further improvements, the chain extender is cetyl trimethoxysiloxane.
Further improved, the stabilizer comprises magnesium stearate and calcium stearate, and the mass ratio of the magnesium stearate to the calcium stearate is 1:1.
Further improvement, the antioxidant comprises an antioxidant 1010 and an antioxidant 168, wherein the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:1.
further improvements, the light stabilizer includes an anti-uv agent 622.
Further improvements, the slip agent includes erucamide.
Further improvements include the surfactants include glyceryl oleate.
Further improved, the amylose content in the starch is more than 60%.
The preparation method of the high heat-resistant thermoplastic starch is characterized by comprising the following steps:
step one, mixing starch and a pre-hydrolyzed chain extender in proportion, putting the mixture into a high-speed stirrer, treating the mixture at 110 ℃ for 15min, cooling the mixture to 60 ℃, continuously adding a stiffening agent, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, a slipping agent and a surfactant to form a mixture, stirring the mixture for 2min, and taking out the mixture to obtain a semi-finished product; the pre-hydrolyzed chain extender is obtained by mixing 1 part by weight of the chain extender, 17 parts by weight of methanol and 2 parts by weight of water and then hydrolyzing for 2-4 hours at normal temperature;
placing the semi-finished product for 4-12h, and putting the semi-finished product into a conical double-screw extruder for extrusion under the following conditions: the temperature is 100-135 ℃, wherein the temperature of the shearing section is 100-105 ℃, the temperature of the extrusion section is 110-130 ℃, the temperature of the machine head and the hot runner is 135 ℃, and the finished product is obtained after extrusion, traction, air cooling and granulating.
The invention has the beneficial effects that:
1. the hexadecyl trimethoxy siloxane is utilized to carry out coupling reaction with hydroxyl on a starch molecular chain, and alkane molecular branched chains with higher stability are grafted on the starch molecular chain, so that the purposes of reducing the molecular chain slippage of thermoplastic starch in a heated state, improving the rheological property of the thermoplastic starch and improving the thermal deformation temperature of a product are achieved.
2. The viscosity of the plasticizer among thermoplastic starch molecules is improved by using a large molecular weight plasticizer (diglycerol and decaglycerol), the rheological property is improved, and the fluidity is reduced.
3. The heat resistance of the thermoplastic starch product is improved by utilizing the action of the strong hydrogen bond compound. The strong electric charge force in the 2-methyl-5-nitroimidazole and the 1-ethyl-3-methyl-dicyandiamide salt reduces the molecular flow between the thermoplastic starch at high temperature and improves the heat distortion temperature and rigidity of the thermoplastic starch.
4. The thermoplastic starch is supported by utilizing rigid powder such as nanocellulose, nano calcium carbonate, whisker, mica powder and the like, and simultaneously hydroxyl groups indicated by the powder can generate electrostatic effect with the thermoplastic starch, so that the heat deformation temperature and rigidity of the thermoplastic starch are improved.
Drawings
The invention is further illustrated by the accompanying drawings, the content of which does not constitute any limitation of the invention.
FIG. 1 is a (partial) comparison of the infrared spectra of comparative examples 1 and 4.
Fig. 2 is a picture of the product of the present invention.
Detailed Description
The invention will be further described in detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the invention more apparent.
The high heat-resistant thermoplastic starch comprises the following raw materials in proportion:
the preparation method comprises the following steps:
1. mixing A and pre-hydrolyzed E in proportion, putting into a high-speed stirrer, processing at 110 ℃ for 15min, cooling to 60 ℃, continuously adding a mixture of C, D single product and B and an auxiliary agent F-J, wherein the mixture of B must contain glycerin, diglycerin and decaglycerin, the stabilizer is magnesium stearate and calcium stearate which are added in a ratio of 1:1, the antioxidant is 1010 and 168 which are added in a ratio of 1:1, and the stabilizer is added in a ratio of total parts.
Stirring the mixture for 2min, and taking out to obtain semi-finished product.
2. Placing the semi-finished product overnight (4-12 h), and putting the semi-finished product into a conical double-screw extruder for extrusion under the following conditions:
the temperature is 100-135 ℃ (shearing section temperature is 100-105 ℃, extrusion section temperature is 110-130 ℃, and the temperature of a machine head and a hot runner is 135 ℃), and the vacuum extraction process is carried out. Extruding, drawing, air cooling and granulating to obtain the finished product.
The finished product has the appearance of light green or light yellow green semitransparent particles, smooth surface, softer surface and unique fragrance of starch, as shown in figure 2.
Comparative example 1:
75phr of corn starch and 25phr of glycerin were mixed, extruded by a conical twin-screw extruder, and pelletized to obtain thermoplastic starch.
Comparative example 2:
75phr of corn starch, 25phr of plasticizer (glycerin 21phr, diglycerin 2phr, decaglycerin 2 phr), 1phr of 2-methyl-5-nitroimidazole, 0.3phr of stabilizer, 0.5phr of antioxidant, 0.5phr of light stabilizer, 0.5phr of erucamide and 0.5phr of oleic acid glyceride.
Comparative example 3:
75phr of corn starch, 25phr of plasticizer (glycerin 21phr, diglycerin 2phr, decaglycerin 2 phr), 2phr of nano calcium carbonate, 0.3phr of stabilizer, 0.5phr of antioxidant, 0.5phr of light stabilizer, 0.5phr of erucamide and 0.5phr of oleic glyceride.
Comparative example 4:
75phr of corn starch, 25phr of plasticizer (glycerin 21phr, diglycerin 2phr, decaglycerin 2 phr), 0.1phr of hexadecyl trimethoxy siloxane, 0.3phr of stabilizer, 0.5phr of antioxidant, 0.5phr of light stabilizer, 0.5phr of erucamide and 0.5phr of oleic acid glyceride.
After the above comparative example was prepared into thermoplastic starch according to the above preparation method, it was mixed with linear low density polyethylene 7042 (produced by petrifaction Dushan mountain petrifaction) according to the following linear low density polyethylene: thermoplastic starch=7:3 was compounded and blended directly, injection molded into bars of 80×10×4mm in size, and tested for flexural strength, flexural modulus and heat distortion temperature.
Example 1:
75phr of corn starch, 25phr of plasticizer (glycerin 21phr, diglycerin 2phr, decaglycerin 2 phr), 1phr of 2-methyl-5-nitroimidazole, 2phr of nano calcium carbonate, 0.1phr of hexadecyl trimethoxy siloxane, 0.3phr of stabilizer, 0.5phr of antioxidant, 0.5phr of light stabilizer, 0.5phr of erucamide and 0.5phr of oleic glyceride.
Example 2:
75phr of corn starch, 25phr of plasticizer (15 phr of glycerin, 5phr of diglycerin and 5phr of decaglycerin), 2phr of 2-methyl-5-nitroimidazole, 5phr of nano calcium carbonate, 0.3phr of hexadecyl trimethoxy siloxane, 0.3phr of stabilizer, 0.5phr of antioxidant, 0.5phr of light stabilizer, 0.5phr of erucamide and 0.5phr of oleic glyceride.
Example 3:
80phr of corn starch, 20phr of plasticizer (16 phr of glycerin, 2phr of diglycerin and 2phr of decaglycerin), 1phr of 2-methyl-5-nitroimidazole, 2phr of mica powder (2000 meshes), 0.1phr of hexadecyl trimethoxy siloxane, 0.3phr of stabilizer, 0.3phr of antioxidant, 0.3phr of light stabilizer, 1.0phr of erucamide and 1.0phr of oleic glyceride.
Example 4:
80phr of corn starch, 20phr of plasticizer (10 phr of glycerin, 5phr of diglycerin and 5phr of decaglycerin), 2phr of 2-methyl-5-nitroimidazole, 5phr of mica powder (2000 meshes), 0.2phr of hexadecyl trimethoxy siloxane, 0.3phr of stabilizer, 0.3phr of antioxidant, 0.3phr of light stabilizer, 1.0phr of erucamide and 1.0phr of oleic glyceride.
After the thermoplastic starch is prepared according to the preparation method, the thermoplastic starch is prepared with linear low density polyethylene 7042 according to the linear low density polyethylene: thermoplastic starch=7:3 was compounded and blended directly, injection molded into bars of 80×10×4mm in size, and tested for flexural strength, flexural modulus and heat distortion temperature.
The testing method comprises the following steps: the flexural strength and flexural modulus were measured according to GB/T9341-2008, the average value of 5 groups of samples was taken, the heat distortion temperature was measured according to GB/T1634.2, the temperature rise rate at the time of the heat distortion temperature measurement was 10 ℃/min, the pressure was 0.45MPa, the number of samples was 2, and the results were averaged.
Physical property meter
Comparative examples 2 to 4 are samples in which 2-methyl-5-nitroimidazole, inorganic powder and chain extender were added separately, and the flexural strength, flexural modulus and heat distortion temperature were all improved to some extent in comparative example 1, of which the effect was the best when 5phr of inorganic powder was added. The above data illustrate that the addition of the above agents alone improves the properties listed for the composite, but the principle is different: 2-methyl-5-nitroimidazole and starch form a reticular cross-linked structure with lorentz force as a dominant component through the interaction between charges; the inorganic powder has the function of reducing the deformation of the matrix; the chain extender can be used for branching starch, and the grafted branched chain is alkane with a C16 composition and plays a role in reducing molecular slippage between starches.
Whereas examples 1 and 2 are samples with small and large amounts of 2-methyl-5-nitroimidazole, inorganic powder and chain extender, respectively, the properties are significantly improved again, and the specific values cannot be considered as simple additions, since the properties of a material are generally not proportional to the addition of modifier in the higher ranges, and therefore the modifier content required for a further improvement of 10% of the properties is far greater than before.
From examples 3 and 4, when the starch content is increased to 80phr and the inorganic powder is replaced by mica powder, various properties are further improved, because 1 and less plasticizers enable the intermolecular force of thermoplastic starch to be larger, the properties of the thermoplastic starch are improved, and 2 and mica powder are sheet materials with higher diameter-thickness ratio, and a better supporting effect can be achieved.
As shown in FIG. 1, it can be seen from the figure that after the addition of the chain extender, the thermoplastic starch is at 2852cm -1 A new infrared absorption peak was generated indicating that the chain extender grafted an alkane branch to the thermoplastic starch.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The high heat-resistant thermoplastic starch is characterized by comprising 100 parts by weight of main materials and 5-12.8 parts by weight of auxiliary materials, wherein the main materials comprise starch and a plasticizer, and the plasticizer comprises glycerol, diglycerol and decaglycerol; the auxiliary materials comprise 2-methyl-5-nitroimidazole, a stiffening agent, a chain extender, a stabilizer, an antioxidant, a light stabilizer, a slipping agent and a surfactant;
the mass ratio range of each raw material in the main material is as follows:
75-80% of starch, 10-16% of glycerol, 2-5% of diglycerol and 2-5% of decaglycerol;
the main materials are used as the reference, and the mass ratio ranges of the raw materials of the auxiliary materials are as follows: comprises 1 to 3 weight parts of 2-methyl-5-nitroimidazole, 2 to 5 weight parts of stiffening agent, 0.1 to 0.3 weight part of chain extender, 0.3 to 0.5 weight part of stabilizer, 0.5 to 1.5 weight parts of antioxidant, 0.1 to 0.5 weight part of light stabilizer, 0.5 to 1 weight part of slipping agent and 0.5 to 1 weight part of surfactant.
2. The high heat resistant thermoplastic starch of claim 1 wherein said stiffening agent is one of nanocellulose, light calcium carbonate and platy mica powder.
3. The high heat resistant thermoplastic starch according to claim 1 wherein said chain extender is hexadecyltrimethoxysiloxane.
4. The high heat resistant thermoplastic starch of claim 1 wherein said stabilizer comprises magnesium stearate and calcium stearate in a mass ratio of 1:1.
5. The high heat resistant thermoplastic starch according to claim 1, wherein the antioxidant comprises an antioxidant 1010 and an antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:1.
6. the high heat resistant thermoplastic starch of claim 1 wherein said light stabilizer comprises an anti-uv agent 622.
7. The high heat resistant thermoplastic starch of claim 1 wherein said slip agent comprises erucamide.
8. The high heat resistant thermoplastic starch of claim 1 wherein said surfactant comprises glycerol oleate.
9. The high heat resistant thermoplastic starch of claim 1 wherein the amylose content of said starch is greater than 60%.
10. A process for the preparation of a highly heat resistant thermoplastic starch as claimed in claim 1, comprising the steps of:
step one, mixing starch and a pre-hydrolyzed chain extender in proportion, putting the mixture into a high-speed stirrer, treating the mixture at 110 ℃ for 15min, cooling the mixture to 60 ℃, continuously adding a stiffening agent, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, a slipping agent and a surfactant to form a mixture, stirring the mixture for 2min, and taking out the mixture to obtain a semi-finished product; the pre-hydrolyzed chain extender is obtained by mixing 1 part by weight of the chain extender, 17 parts by weight of methanol and 2 parts by weight of water and then hydrolyzing for 2-4 hours at normal temperature;
placing the semi-finished product for 4-12h, and putting the semi-finished product into a conical double-screw extruder for extrusion under the following conditions: the temperature is 100-135 ℃, wherein the temperature of the shearing section is 100-105 ℃, the temperature of the extrusion section is 110-130 ℃, the temperature of the machine head and the hot runner is 135 ℃, and the finished product is obtained after extrusion, traction, air cooling and granulating.
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