CN113667190A - Biodegradable modified starch-based toy material and preparation method of toy thereof - Google Patents
Biodegradable modified starch-based toy material and preparation method of toy thereof Download PDFInfo
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- CN113667190A CN113667190A CN202110540051.3A CN202110540051A CN113667190A CN 113667190 A CN113667190 A CN 113667190A CN 202110540051 A CN202110540051 A CN 202110540051A CN 113667190 A CN113667190 A CN 113667190A
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- 239000004368 Modified starch Substances 0.000 title claims abstract description 55
- 229920000881 Modified starch Polymers 0.000 title claims abstract description 55
- 235000019426 modified starch Nutrition 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 229920002472 Starch Polymers 0.000 claims abstract description 43
- 235000019698 starch Nutrition 0.000 claims abstract description 43
- 239000008107 starch Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000003607 modifier Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 19
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 10
- 239000004626 polylactic acid Substances 0.000 claims abstract description 10
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims abstract description 8
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 8
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims abstract description 8
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000010010 raising Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002347 injection Methods 0.000 claims description 32
- 239000007924 injection Substances 0.000 claims description 32
- 238000001746 injection moulding Methods 0.000 claims description 23
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 14
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000704 biodegradable plastic Polymers 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 27
- 229920003023 plastic Polymers 0.000 abstract description 27
- 238000001125 extrusion Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/06—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a biodegradable modified starch-based toy material and a preparation method of the toy, which comprises the following steps: adding 5-8 parts by weight of gadolinium chloride, 2-4 parts by weight of cerium chloride and 6-12 parts by weight of yttrium chloride into 50-70 parts by weight of water, then adding 4-8 parts by weight of naphthenic acid and 2-12 parts by weight of isooctanoic acid into the water, uniformly mixing and stirring, raising the temperature of a mixed solution to 70-85 ℃, then preserving the heat for 1-2 hours, then cooling to room temperature, continuously adding 2-5 parts by weight of polyethyleneimine and 2-5 parts by weight of polyethanolamine into the mixed solution, uniformly mixing and stirring to obtain a modifier; mixing starch and a modifier at 70-100 ℃ to obtain thermoplastic modified starch; thermoplastic modified starch, polylactic acid, an antioxidant, a plasticizer and a stabilizer are added into a high-speed mixer for mixing, and a three-screw extruder is adopted for extrusion, cooling, drying and granulating. The method effectively improves the processing and forming performance and the water resistance of the starch-based toy material, so that the biodegradable starch-based plastic toy with excellent breaking strength is prepared.
Description
Technical Field
The invention relates to a starch-based toy material, in particular to a biodegradable modified starch-based toy material and a preparation method of a toy thereof.
Background
Starch-based plastics are currently the major biodegradable plastics used in a large number of various packaging plastic products. The starch-based plastic is a plastic product which is prepared by taking starch as a main raw material, modifying and plasticizing the starch and then blending the starch with other polymers. However, starch is a natural high molecular polymer, and the molecules of the starch contain a large number of hydroxyl groups (molecular structures II and III), so that the interaction force between starch macromolecules is strong, and therefore, the starch does not have thermoplasticity, is difficult to form and process, and has poor water resistance. Therefore, the compatibility of starch and base resin is poor, the processing and forming performance of the material is affected, the existing common solution is to use a small-molecular polar plasticizer for thermoplastic treatment, but the water resistance of the obtained starch-based plastic is still poor. Therefore, the toy made of the existing starch-based plastic has poor water resistance, the service life of the toy after being soaked in water is shortened rapidly, the use feeling and the experience effect are influenced, and the oxidation resistance and the corrosion resistance are obviously insufficient. In addition, the existing starch-based plastic is easy to age and difficult to recover, so that the cost is high, and the popularization is greatly limited.
Disclosure of Invention
The invention aims to provide a biodegradable modified starch-based toy material, which improves the processing and forming properties and the water resistance of the starch-based toy material.
Another object of the present invention is to provide a method for preparing a toy from a biodegradable modified starch-based toy material.
In order to realize the first invention, the following technical scheme is adopted:
a biodegradable modified starch-based toy material is prepared by the following steps:
(1) adding 5-8 parts by weight of gadolinium chloride, 2-4 parts by weight of cerium chloride and 6-12 parts by weight of yttrium chloride into 50-70 parts by weight of water, then adding 4-8 parts by weight of naphthenic acid and 2-12 parts by weight of isooctanoic acid into the water, uniformly mixing and stirring, raising the temperature of a mixed solution to 70-85 ℃, carrying out heat preservation treatment for 1-2 hours, then cooling to room temperature, continuously adding 2-5 parts by weight of polyethyleneimine and 2-5 parts by weight of polyethanolamine into the mixed solution, uniformly mixing and stirring to obtain a modifier;
(2) adding starch and a modifier into an internal mixer, and mixing at 70-100 ℃ to prepare thermoplastic modified starch;
(3) adding thermoplastic modified starch, polylactic acid, an antioxidant, a plasticizer and a stabilizer into a high-speed mixer, uniformly mixing, extruding by a three-screw extruder, cooling, drying and granulating to obtain the modified starch-based toy material.
The proportion of the starch to the modifier in the step (2) is respectively 92-95 parts and 5-8 parts by weight.
The proportions of the thermoplastic modified starch, the polylactic acid, the antioxidant, the plasticizer and the stabilizer in the step (3) are respectively 60-70 parts, 30-35 parts, 0.1-0.3 part, 0.5-2 parts and 0.2-0.4 part by weight.
The barrel temperature of the three-screw extruder is as follows: the front section is 100-120 ℃, the middle section is 130-150 ℃, and the rear section is 150-180 ℃; the rotating speed of the screw is 12-20 r/min, and the pressure is 5-10 MPa.
The antioxidant is one or more of phosphite ester, 2, 6-di-tert-butylphenol, thiopropionate and bis-salicylidene diamine.
The plasticizer is one or more of dioctyl phthalate and dibutyl phthalate.
The stabilizer is one or more of isooctanoic acid, calcium isooctanoate and zinc isooctanoate.
Further, the antioxidant is 2, 6-di-tert-butylphenol, the plasticizer is dibutyl phthalate, and the stabilizer is zinc isooctanoate.
In order to realize the second invention, the following technical scheme is adopted:
a method for preparing a toy by adopting biodegradable modified starch-based toy material comprises the following steps:
(1) injecting the modified starch-based toy material into a storage barrel of an injection molding machine, setting the heating temperature of a screw in the storage barrel to be 70-135 ℃, extruding and melting the injection molding raw material, and maintaining the injection molding raw material in a molten state; then adjusting the temperature of the fixed die and the movable die to 30-60 ℃; setting the injection pressure to be 50-120bar, the injection time to be 2-6s and the injection speed to be 500-800mm/s, and injecting after the die is closed;
(2) entering a pressure maintaining state after the injection is finished, and setting the pressure maintaining pressure to be 90-120bar and the pressure maintaining time to be 1-3 s; cooling for 4-15s after the pressure maintaining is finished; and opening the mold, and taking out the product after demolding to obtain the biodegradable plastic toy.
The invention has the following beneficial effects:
according to the invention, the starch is mixed and esterified by adopting the modifier, so that the starch has thermoplasticity, the processing and forming performance of the starch-based toy material is improved, and the toy with excellent performance can be obtained through extrusion and injection molding processes; meanwhile, the mechanical property and the water resistance of the starch-based toy material are improved, and the oxidation resistance and the corrosion resistance of the starch-based toy material are also improved.
The biodegradable starch-based plastic toy product with excellent breaking strength and high density can be obtained by adopting specific component proportion and injection molding process parameters.
The starch-based toy material and the toy prepared by the method have excellent performance, so that the cost is lower compared with the existing starch-based plastic, and the starch-based toy material and the toy are suitable for large-scale industrial production.
Detailed Description
The following examples are only for illustrating the present invention, and the scope of the present invention is not limited to only the following examples. The objectives of the present invention can be achieved by the ordinary skilled person in the art according to the disclosure of the present invention and the ranges of the parameters.
Example 1
A biodegradable modified starch-based toy material is prepared by the following steps:
(1) adding 5 parts of gadolinium chloride, 4 parts of cerium chloride and 7 parts of yttrium chloride into 70 parts of water by weight, then adding 5 parts of naphthenic acid and 3 parts of isooctanoic acid into the water, uniformly mixing and stirring, raising the temperature of a mixed solution to 70 ℃, carrying out heat preservation treatment for 1 hour, then cooling to room temperature, continuously adding 3 parts of polyethyleneimine and 3 parts of polyethanolamine into the mixed solution, and uniformly mixing and stirring to obtain a starch modifier;
(2) adding 94 parts of starch and 6 parts of modifier into an internal mixer, and mixing at 80 ℃ to prepare thermoplastic modified starch;
(3) adding 64.5 parts by weight of thermoplastic modified starch, 33 parts by weight of polylactic acid, 0.3 part by weight of antioxidant, 0.5 part by weight of plasticizer and 0.2 part by weight of stabilizer into a high-speed mixer, uniformly mixing, extruding by a three-screw extruder, cooling, drying and granulating to obtain a modified starch-based toy material; the extruder parameters were as follows: barrel temperature: the front section is 110 ℃, the middle section is 140 ℃ and the rear section is 170 ℃; the rotating speed of the screw is 18r/min, and the pressure is 8 MPa.
Wherein the antioxidant adopts 2, 6-di-tert-butylphenol; the plasticizer adopts dibutyl phthalate; the stabilizer adopts zinc isooctoate.
The toy is prepared by adopting the modified starch-based toy material:
(1) drying the dried modified plastic particles for 1h at 100 ℃, injecting the dried modified plastic particles into a storage barrel of an injection molding machine, setting the heating temperature of a screw in the storage barrel to be 105 ℃, extruding and melting the injection molding raw materials, and maintaining the injection molding raw materials in a molten state; then adjusting the temperature of the fixed die and the movable die to 40 ℃; setting the injection pressure to be 80bar, the injection time to be 5s and the injection speed to be 600mm/s, and injecting after the die is closed;
(2) after the injection is finished, the injection enters a pressure maintaining state, the pressure maintaining pressure is set to be 110bar, and the pressure maintaining time is set to be 2 s; cooling for 5s after the pressure maintaining is finished; and opening the mold, and taking out the product after demolding to obtain the biodegradable modified plastic toy.
Example 2
A biodegradable modified starch-based toy material is prepared by the following steps:
(1) adding 6 parts by weight of gadolinium chloride, 4 parts by weight of cerium chloride and 6 parts by weight of yttrium chloride into 70 parts by weight of water, then adding 5 parts by weight of naphthenic acid and 4 parts by weight of isooctanoic acid into the water, uniformly mixing and stirring, raising the temperature of a mixed solution to 70 ℃, carrying out heat preservation treatment for 1 hour, then cooling to room temperature, continuously adding 2 parts by weight of polyethyleneimine and 3 parts by weight of polyethanolamine into the mixed solution, and uniformly mixing and stirring to obtain a starch modifier;
(2) adding 93 parts of starch and 7 parts of modifier into an internal mixer, and mixing at 90 ℃ to prepare thermoplastic modified starch;
(3) adding 65 parts by weight of thermoplastic modified starch, 34.5 parts by weight of polylactic acid, 0.2 part by weight of antioxidant, 0.5 part by weight of plasticizer and 0.3 part by weight of stabilizer into a high-speed mixer, uniformly mixing, extruding by using a three-screw extruder, cooling, drying and granulating to obtain a modified starch-based toy material; the extruder parameters were as follows: barrel temperature: the front section is 115 ℃, the middle section is 145 ℃ and the rear section is 165 ℃; the rotating speed of the screw is 16r/min, and the pressure is 7 MPa.
Wherein the antioxidant adopts 2, 6-di-tert-butylphenol; the plasticizer adopts dibutyl phthalate; the stabilizer adopts zinc isooctoate.
The toy is prepared by adopting the modified starch-based toy material:
(1) drying the dried modified plastic particles for 2h at 100 ℃, injecting the dried modified plastic particles into a storage barrel of an injection molding machine, setting the heating temperature of a screw in the storage barrel to be 105 ℃, extruding and melting the injection molding raw materials, and maintaining the injection molding raw materials in a molten state; then adjusting the temperature of the fixed die and the movable die to 40 ℃; setting the injection pressure to be 80bar, the injection time to be 5s and the injection speed to be 600mm/s, and injecting after the die is closed;
(2) after the injection is finished, the injection enters a pressure maintaining state, the pressure maintaining pressure is set to be 100bar, and the pressure maintaining time is set to be 1 s; cooling for 5s after the pressure maintaining is finished; and opening the mold, and taking out the product after demolding to obtain the biodegradable modified plastic toy.
Example 3
A biodegradable modified starch-based toy material is prepared by the following steps:
(1) adding 7 parts by weight of gadolinium chloride, 3 parts by weight of cerium chloride and 8 parts by weight of yttrium chloride into 70 parts by weight of water, then adding 4 parts by weight of naphthenic acid and 2 parts by weight of isooctanoic acid into the water, uniformly mixing and stirring, raising the temperature of a mixed solution to 70 ℃, carrying out heat preservation treatment for 1 hour, then cooling to room temperature, continuously adding 2 parts by weight of polyethyleneimine and 4 parts by weight of polyethanolamine into the mixed solution, and uniformly mixing and stirring to obtain a starch modifier;
(2) adding 93 parts of starch and 7 parts of modifier into an internal mixer, and mixing at 95 ℃ to prepare thermoplastic modified starch;
(3) adding 65 parts by weight of thermoplastic modified starch, 34.5 parts by weight of polylactic acid, 0.2 part by weight of antioxidant, 0.5 part by weight of plasticizer and 0.3 part by weight of stabilizer into a high-speed mixer, uniformly mixing, extruding by using a three-screw extruder, cooling, drying and granulating to obtain the modified starch-based toy material extruder, wherein the parameters of the extruder are as follows: barrel temperature: the front section is 120 ℃, the middle section is 150 ℃, and the rear section is 180 ℃; the rotating speed of the screw is 20r/min, and the pressure is 10 MPa.
Wherein the antioxidant adopts 2, 6-di-tert-butylphenol; the plasticizer adopts dibutyl phthalate; the stabilizer adopts zinc isooctoate.
The toy is prepared by adopting the modified starch-based toy material:
(1) drying the dried modified plastic particles for 3h at 100 ℃, injecting the dried modified plastic particles into a storage barrel of an injection molding machine, setting the heating temperature of a screw in the storage barrel to be 110 ℃, extruding and melting the injection molding raw materials, and maintaining the injection molding raw materials in a molten state; then adjusting the temperature of the fixed die and the movable die to 40 ℃; setting the injection pressure to be 100bar, the injection time to be 6s and the injection speed to be 700mm/s, and injecting after the die is closed;
(2) after the injection is finished, the injection enters a pressure maintaining state, the pressure maintaining pressure is set to be 100bar, and the pressure maintaining time is set to be 1 s; cooling for 5s after the pressure maintaining is finished; and opening the mold, and taking out the product after demolding to obtain the biodegradable modified plastic toy.
Example 4
A biodegradable modified starch-based toy material is prepared by the following steps:
(1) adding 8 parts of gadolinium chloride, 2 parts of cerium chloride and 6 parts of yttrium chloride into 70 parts of water, then adding 8 parts of naphthenic acid and 2 parts of isooctanoic acid into the water, uniformly mixing and stirring, raising the temperature of a mixed solution to 85 ℃, carrying out heat preservation treatment for 1 hour, then cooling to room temperature, continuously adding 5 parts of polyethyleneimine and 2 parts of polyethanolamine into the mixed solution, and uniformly mixing and stirring to obtain a starch modifier;
(2) adding 92 parts of starch and 8 parts of modifier into an internal mixer, and mixing at 70 ℃ to prepare thermoplastic modified starch;
(3) adding 60 parts by weight of thermoplastic modified starch, 35 parts by weight of polylactic acid, 0.3 part by weight of antioxidant, 0.5 part by weight of plasticizer and 0.4 part by weight of stabilizer into a high-speed mixer, uniformly mixing, adopting a three-screw extruder, cooling, drying and granulating after extrusion to obtain the modified starch-based toy material extruder, wherein the parameters of the extruder are as follows: barrel temperature: the front section is 120 ℃, the middle section is 150 ℃, and the rear section is 180 ℃; the rotating speed of the screw is 12r/min, and the pressure is 5 MPa.
Wherein the antioxidant adopts phosphite ester and 2, 6-di-tert-butylphenol; the plasticizer adopts dibutyl phthalate; isooctanoic acid is used as a stabilizer.
The toy is prepared by adopting the modified starch-based toy material:
(1) drying the dried modified plastic particles for 3h at 100 ℃, injecting the dried modified plastic particles into a storage barrel of an injection molding machine, setting the heating temperature of a screw in the storage barrel to be 135 ℃, extruding and melting the injection molding raw materials, and maintaining the injection molding raw materials in a molten state; then adjusting the temperature of the fixed die and the movable die to 60 ℃; setting the injection pressure to be 50bar, the injection time to be 2s and the injection speed to be 500mm/s, and injecting after the die is closed;
(2) after the injection is finished, the injection enters a pressure maintaining state, the pressure maintaining pressure is set to be 90bar, and the pressure maintaining time is set to be 1 s; cooling for 15s after the pressure maintaining is finished; and opening the mold, and taking out the product after demolding to obtain the biodegradable modified plastic toy.
Example 5
A biodegradable modified starch-based toy material is prepared by the following steps:
(1) adding 5 parts by weight of gadolinium chloride, 4 parts by weight of cerium chloride and 12 parts by weight of yttrium chloride into 50 parts by weight of water, then adding 4 parts by weight of naphthenic acid and 12 parts by weight of isooctanoic acid into the water, uniformly mixing and stirring, raising the temperature of a mixed solution to 85 ℃, carrying out heat preservation treatment for 2 hours, then cooling to room temperature, continuously adding 2 parts by weight of polyethyleneimine and 5 parts by weight of polyethanolamine into the mixed solution, and uniformly mixing and stirring to obtain a modifier of starch;
(2) according to the parts by weight, 95 parts of starch and 5 parts of modifier are added into an internal mixer and mixed at 100 ℃ to prepare thermoplastic modified starch;
(3) adding 70 parts by weight of thermoplastic modified starch, 30 parts by weight of polylactic acid, 0.1 part by weight of antioxidant, 2 parts by weight of plasticizer and 0.2 part by weight of stabilizer into a high-speed mixer, uniformly mixing, adopting a three-screw extruder, and cooling, drying and granulating after extrusion to obtain the modified starch-based toy material extruder with the following parameters: barrel temperature: the front section is 100 ℃, the middle section is 130 ℃ and the rear section is 150 ℃; the rotating speed of the screw is 20r/min, and the pressure is 10 MPa.
Wherein the antioxidant adopts thiopropionate and bis-salicylidene diamine; the plasticizer is dioctyl phthalate; the stabilizer adopts calcium isooctanoate and zinc isooctanoate.
The toy is prepared by adopting the modified starch-based toy material:
(1) drying the dried modified plastic particles for 3h at 100 ℃, injecting the dried modified plastic particles into a storage barrel of an injection molding machine, setting the heating temperature of a screw in the storage barrel to be 70 ℃, and extruding and melting injection molding raw materials and maintaining the injection molding raw materials in a molten state; then adjusting the temperature of the fixed die and the movable die to 30 ℃; setting the injection pressure to be 120bar, the injection time to be 6s and the injection speed to be 800mm/s, and injecting after the die is closed;
(2) entering a pressure maintaining state after the injection is finished, and setting the pressure maintaining pressure to be 120bar and the pressure maintaining time to be 3 s; cooling for 4s after the pressure maintaining is finished; and opening the mold, and taking out the product after demolding to obtain the biodegradable modified plastic toy.
The biodegradable modified starch-based toy materials of examples 1-3 were tested for breaking strength and elongation at break according to the test methods for tensile Properties of plastics GB/T1040-92, the results of which are given in the following table.
The comparative example is a common starch-based plastic, and from the results in the table above, it can be seen that the materials of examples 1-3 both have better breaking strength and elongation at break than the comparative example; after 48 hours of immersion, the breaking strength and elongation at break of the materials of examples 1-3 were still at the same level before immersion, whereas the values of breaking strength and elongation at break of the comparative example material were reduced after immersion, in particular the breaking strength was significantly reduced. The above results demonstrate that the method of the present invention effectively improves the mechanical properties and water resistance of starch-based toy materials, and that the improvement in mechanical properties also manifests itself in improved oxidation resistance and corrosion resistance.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments of the present invention are to be considered in all respects as illustrative and not restrictive. Therefore, any minor modifications, equivalent changes and modifications to the above embodiments according to the spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (9)
1. A biodegradable modified starch-based toy material, characterized in that: the preparation method comprises the following steps:
(1) adding 5-8 parts by weight of gadolinium chloride, 2-4 parts by weight of cerium chloride and 6-12 parts by weight of yttrium chloride into 50-70 parts by weight of water, then adding 4-8 parts by weight of naphthenic acid and 2-12 parts by weight of isooctanoic acid into the water, uniformly mixing and stirring, raising the temperature of a mixed solution to 70-85 ℃, carrying out heat preservation treatment for 1-2 hours, then cooling to room temperature, continuously adding 2-5 parts by weight of polyethyleneimine and 2-5 parts by weight of polyethanolamine into the mixed solution, uniformly mixing and stirring to obtain a modifier;
(2) adding starch and a modifier into an internal mixer, and mixing at 70-100 ℃ to prepare thermoplastic modified starch;
(3) adding thermoplastic modified starch, polylactic acid, an antioxidant, a plasticizer and a stabilizer into a high-speed mixer, uniformly mixing, extruding by a three-screw extruder, cooling, drying and granulating to obtain the modified starch-based toy material.
2. The biodegradable modified starch-based toy material according to claim 1, characterized in that: the proportion of the starch to the modifier in the step (2) is respectively 92-95 parts and 5-8 parts by weight.
3. The biodegradable modified starch-based toy material according to claim 2, characterized in that: the proportions of the thermoplastic modified starch, the polylactic acid, the antioxidant, the plasticizer and the stabilizer in the step (3) are respectively 60-70 parts, 30-35 parts, 0.1-0.3 part, 0.5-2 parts and 0.2-0.4 part by weight.
4. A biodegradable modified starch-based toy material according to claim 3, characterized in that: the antioxidant is one or more of phosphite ester, 2, 6-di-tert-butylphenol, thiopropionate and bis-salicylidene diamine.
5. The biodegradable modified starch-based toy material according to claim 4, characterized in that: the plasticizer is one or more of dioctyl phthalate and dibutyl phthalate.
6. The biodegradable modified starch-based toy material according to claim 5, characterized in that: the stabilizer is one or more of isooctanoic acid, calcium isooctanoate and zinc isooctanoate.
7. The biodegradable modified starch-based toy material according to claim 6, characterized in that: the antioxidant is 2, 6-di-tert-butylphenol, the plasticizer is dibutyl phthalate, and the stabilizer is zinc isooctanoate.
8. The biodegradable modified starch-based toy material according to claim 1, characterized in that: the barrel temperature of the three-screw extruder is as follows: the front section is 100-120 ℃, the middle section is 130-150 ℃, and the rear section is 150-180 ℃; the rotating speed of the screw is 12-20 r/min, and the pressure is 5-10 MPa.
9. A method of making a toy using the biodegradable modified starch-based toy material according to any one of claims 1-8, characterized in that: the method comprises the following steps:
(1) injecting the modified starch-based toy material into a storage barrel of an injection molding machine, setting the heating temperature of a screw in the storage barrel to be 70-135 ℃, extruding and melting the injection molding raw material, and maintaining the injection molding raw material in a molten state; then adjusting the temperature of the fixed die and the movable die to 30-60 ℃; setting the injection pressure to be 50-120bar, the injection time to be 2-6s and the injection speed to be 500-800mm/s, and injecting after the die is closed;
(2) entering a pressure maintaining state after the injection is finished, and setting the pressure maintaining pressure to be 90-120bar and the pressure maintaining time to be 1-3 s; cooling for 4-15s after pressure maintaining; and opening the mold, and taking out the product after demolding to obtain the biodegradable plastic toy.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003687A (en) * | 2006-12-18 | 2007-07-25 | 江南大学 | Environmental protective type liquid composite thermal stabilizer, and preparation method |
| CN101353400A (en) * | 2008-09-11 | 2009-01-28 | 四川大学 | Preparation of biodegradable thermoplastic starch plastic having high starch content |
| CN102604346A (en) * | 2012-02-28 | 2012-07-25 | 中国地质大学（武汉） | Biodegradable polylactic acid-starch flame retardant composite material and preparation method thereof |
| CN103819754A (en) * | 2014-02-19 | 2014-05-28 | 福建工程学院 | High toughness starch based thermoplastic plastic and its preparation method |
| CN106188949A (en) * | 2016-07-14 | 2016-12-07 | 天津儒创新材料科技有限公司 | A kind of liquid type rare earth complex heat stabilizer |
| CN106397908A (en) * | 2016-08-31 | 2017-02-15 | 安徽中科自动化股份有限公司 | Plastic agricultural film |
| CN108676609A (en) * | 2018-06-12 | 2018-10-19 | 界首市皖俊轴承有限公司 | A kind of preparation method of Totally synthesized cutting fluid |
| CN108752646A (en) * | 2018-06-19 | 2018-11-06 | 界首市诚信玩具有限公司 | A kind of preparation method of water-fast degradable plastic toy |
| CN108864507A (en) * | 2018-07-10 | 2018-11-23 | 安徽省星年华电器有限公司 | A kind of polyurethane seal strip for refrigerator door production technology |
| CN108929611A (en) * | 2018-08-30 | 2018-12-04 | 郭平 | A kind of mould proof preparation method except aldehyde algae clay interior wall coating |
| CN112297332A (en) * | 2020-08-26 | 2021-02-02 | 苏州东昊塑胶五金有限公司 | Degradable plastic injection molding process and application |
| CN112608543A (en) * | 2020-12-16 | 2021-04-06 | 江苏赛尔密封科技股份有限公司 | High-temperature-resistant polyethylene environment-friendly sealing plate and preparation method thereof |
-
2021
- 2021-05-18 CN CN202110540051.3A patent/CN113667190A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003687A (en) * | 2006-12-18 | 2007-07-25 | 江南大学 | Environmental protective type liquid composite thermal stabilizer, and preparation method |
| CN101353400A (en) * | 2008-09-11 | 2009-01-28 | 四川大学 | Preparation of biodegradable thermoplastic starch plastic having high starch content |
| CN102604346A (en) * | 2012-02-28 | 2012-07-25 | 中国地质大学（武汉） | Biodegradable polylactic acid-starch flame retardant composite material and preparation method thereof |
| CN103819754A (en) * | 2014-02-19 | 2014-05-28 | 福建工程学院 | High toughness starch based thermoplastic plastic and its preparation method |
| CN106188949A (en) * | 2016-07-14 | 2016-12-07 | 天津儒创新材料科技有限公司 | A kind of liquid type rare earth complex heat stabilizer |
| CN106397908A (en) * | 2016-08-31 | 2017-02-15 | 安徽中科自动化股份有限公司 | Plastic agricultural film |
| CN108676609A (en) * | 2018-06-12 | 2018-10-19 | 界首市皖俊轴承有限公司 | A kind of preparation method of Totally synthesized cutting fluid |
| CN108752646A (en) * | 2018-06-19 | 2018-11-06 | 界首市诚信玩具有限公司 | A kind of preparation method of water-fast degradable plastic toy |
| CN108864507A (en) * | 2018-07-10 | 2018-11-23 | 安徽省星年华电器有限公司 | A kind of polyurethane seal strip for refrigerator door production technology |
| CN108929611A (en) * | 2018-08-30 | 2018-12-04 | 郭平 | A kind of mould proof preparation method except aldehyde algae clay interior wall coating |
| CN112297332A (en) * | 2020-08-26 | 2021-02-02 | 苏州东昊塑胶五金有限公司 | Degradable plastic injection molding process and application |
| CN112608543A (en) * | 2020-12-16 | 2021-04-06 | 江苏赛尔密封科技股份有限公司 | High-temperature-resistant polyethylene environment-friendly sealing plate and preparation method thereof |
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Application publication date: 20211119 |