CN113308045B - Anti-aging plastic box and preparation method thereof - Google Patents

Anti-aging plastic box and preparation method thereof Download PDF

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CN113308045B
CN113308045B CN202110591623.0A CN202110591623A CN113308045B CN 113308045 B CN113308045 B CN 113308045B CN 202110591623 A CN202110591623 A CN 202110591623A CN 113308045 B CN113308045 B CN 113308045B
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aging
plastic box
antioxidant
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modified starch
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CN113308045A (en
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马甫海
冯健立
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Ningbo Xinsheng Industrial Enterprise Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16Fibres; Fibrils

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Abstract

The application relates to the technical field of plastic production processes, and particularly discloses an anti-aging plastic box and a preparation method thereof. The anti-aging plastic box is mainly prepared from the following raw materials in parts by weight: modified starch, polypropylene, PE wax, cellulose fiber, an antioxidant and an anti-aging agent; the preparation method of the anti-aging plastic box comprises the following steps: s1, uniformly mixing modified starch, polypropylene, PE (polyethylene) wax, cellulose fibers, an antioxidant and an anti-aging agent according to the proportion to obtain a mixture; s2, extruding the mixture prepared in the step S1 at 190-230 ℃, and performing injection molding to obtain the material. The application makes plastic case ageing resistance effect preferred of ageing resistance.

Description

Anti-aging plastic box and preparation method thereof
Technical Field
The application relates to the technical field of plastic production, in particular to an anti-aging plastic box and a preparation method thereof.
Background
In daily life, the plastic box is used as a container, and the use frequency is high. The plastic box is mainly made of high polymer materials, such as polyethylene, polypropylene materials and the like, the high polymer materials are easily influenced by external factors such as heat, light, thermal oxygen, acid, oxygen and the like in the using process, the performance is poor due to the structural characteristics and physical states of the high polymer materials, such as yellowing, and the mechanical properties such as impact strength, tensile strength, elongation and the like are greatly reduced, so that the normal use of the high polymer materials is influenced. These conditions can occur during various stages of synthesis, storage, processing, etc. of the polymeric material, resulting in the end of the useful life of the material and the disposal of a large quantity of the material.
The poor ageing resistance of plastics results in a relatively short life of the relevant products and facilities of the plastics and requires regular replacement. The existing anti-aging plastic box is usually added with an anti-aging agent in the preparation process, so that active free radicals generated in the plastic due to external factors are continuously absorbed, and molecular fracture or molecular combination is reduced, so that the aging of the plastic is delayed.
Disclosure of Invention
In order to improve the anti-aging performance of the plastic box, the application provides the anti-aging plastic box and the preparation method thereof.
In a first aspect, the application provides an anti-aging plastic box, which adopts the following technical scheme:
an anti-aging plastic box is mainly prepared from the following raw materials in parts by weight: 10-20 parts of modified starch, 70-80 parts of polypropylene, 1-5 parts of PE (polyethylene) wax, 10-15 parts of cellulose fiber, 5-10 parts of antioxidant and 3-5 parts of anti-aging agent, wherein the antioxidant consists of a main antioxidant and an auxiliary antioxidant according to the mass ratio of (2-3) to (1-2), the main antioxidant is at least two of 2, 6-di-tert-butyl-4-hydroxymethylphenol, isocyanate and N, N '- (p-phenylene) bismaleimide, the auxiliary antioxidant is at least two of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, N' -1, 4-phenylene bismaleimide and bis (octadecyl) pentaerythritol diphosphite, and the anti-aging agent is didodecyl thiodipropionate, bis (octadecyl) terephthalate, bis (octadecyl) pentaerythritol diphosphite, At least two of zinc diethyldithiocarbamate and N, N-diacetyl thiodipropionyl dihydrazide, wherein the modified starch is sodium hexametaphosphate modified starch.
By adopting the technical scheme, the modified starch forms a macromolecular cross-linked structure under the action of sodium hexametaphosphate, so that the degradability of the material is enhanced, the environment is protected, 2, 6-di-tert-butyl-4-hydroxymethylphenol in the main antioxidant is easy to volatilize, the physical loss is large, the relative molecular mass of the 2, 6-di-tert-butyl-4-hydroxymethylphenol can be improved by adding isocyanate, the antioxidant effect of the main antioxidant is improved, bis (octadecyl) pentaerythritol diphosphite in the auxiliary antioxidant is easy to hydrolyze, the hydrolysis sensitivity of the bis (octadecyl) pentaerythritol diphosphite can be reduced by adding N, N' -1, 4-phenylene dimaleimide, the auxiliary antioxidant and the main antioxidant are matched with each other, and the modified starch acts in plastics from the aspects of blocking of free radicals and transferring of the free radicals, therefore, the processing performance of the plastic is improved, the aging speed of the plastic box is reduced, the aging resistance of the plastic box is further improved, the zinc diethyldithiocarbamate serving as an accelerant can promote absorption of active free radicals generated in the plastic by the didodecyl thiodipropionate and the N, N-diacetyl thiodipropionyl dihydrazide, the aging resistance effect is improved, the anti-aging agent is more compatible with other substances, the aging speed of the plastic is reduced, the tensile strength and the impact strength of the product are enhanced simultaneously, and the aging resistance effect of the product is further enhanced.
Preferably, the anti-aging agent consists of didodecyl thiodipropionate, zinc diethyldithiocarbamate and N, N-diacetyl thiodipropionyl dihydrazide in a mass ratio of (2-5): 3-8): 5-9.
By adopting the technical scheme, the zinc diethyldithiocarbamate can increase two other anti-aging agents which can promote the compounding of the didodecyl thiodipropionate, the zinc diethyldithiocarbamate and the N, N-diacetyl thiodipropionyl dihydrazide so as to improve the absorption of active free radicals generated in the high polymer material, thereby reducing the occurrence of the condition that the high polymer material has molecular fracture or molecular recombination, and simultaneously the preferable proportion of the three anti-aging agents ensures that the tensile strength and the impact strength of the product can meet the current requirements on the product.
Preferably, the primary antioxidant consists of 2, 6-di-tert-butyl-4-hydroxymethylphenol, isocyanate and N, N '- (p-phenylene) bismaleimide according to the mass ratio of (3-5) to (4-8) to (6-9), and the secondary antioxidant consists of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, N' -1, 4-phenylene bismaleimide and bis (octadecyl) pentaerythritol diphosphite according to the mass ratio of (2-3) to (3-5) to (5-7).
By adopting the technical scheme, the content of N, N ' - (p-phenylene) bismaleimide is higher than that of other two main antioxidants, the loss of 2, 6-di-tert-butyl-4-hydroxymethylphenol in the preparation process is larger due to greater volatilization loss, the loss condition of 2, 6-di-tert-butyl-4-hydroxymethylphenol can be improved by adding isocyanate, the stability of the antioxidant can be improved by adding N, N ' - (p-phenylene) bismaleimide, the bis (octadecyl) pentaerythritol diphosphite is easy to hydrolyze, the hydrolysis sensitivity can be reduced by adding N, N ' -1, 4-phenylene bismaleimide, the molecular weight of the bis (octadecyl) pentaerythritol diphosphite is improved, the volatility is reduced, and the melting point of the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is further reduced by adding the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite The melting temperature, the melt strength and the processability are improved.
Preferably, the cellulose fibers are obtained by treating wood fibers with a titanate coupling agent.
By adopting the technical scheme, the wood fiber is convenient to obtain, the application range is wide, the degradability is good, the main component of the wood fiber is cellulose, the cellulose contains a large amount of hydroxyl, and the hydroxyl forms intermolecular hydrogen bonds or intramolecular hydrogen bonds, so that the wood fiber can absorb water easily, meanwhile, the polarity is strong, most of plastic products are nonpolar and hydrophobic, therefore, the compatibility of the wood fiber and the plastic is poor, the interface cohesive force is small, and the compatibility of the wood fiber and the plastic can be improved by adding the titanate coupling agent.
Preferably, the relative molecular mass of the polypropylene is 150000-.
By adopting the technical scheme, the polypropylene has large relative molecular mass, the branching degree on a molecular chain is smaller, the weak links of the chain structure are fewer, the degradation is not easy, the stability is high, the viscosity is low, and the excellent characteristics of good impact property and high tensile strength are realized, so that the prepared plastic box has better quality and stronger thermal stability.
Preferably, the raw materials further comprise 1-3 parts by weight of plasticizer, and the plasticizer is at least two of trioctyl trimellitate, tributyl citrate and epoxy fatty acid butyl ester.
By adopting the technical scheme, the plasticizer can improve the toughness of a product base material, improve the tensile strength of a product and simultaneously improve the processability of plastics, trioctyl trimellitate has strong heat resistance and processability, tributyl citrate has good compatibility and high plasticizing efficiency, epoxy fatty acid butyl ester is a novel environment-friendly plasticizer and has the advantages of no toxicity, good compatibility, low volatility and the like, and the trioctyl trimellitate, the tributyl citrate and the epoxy fatty acid butyl ester are compounded for use, so that all components in a plastic box product can be more compatible, the heat resistance is stronger, and the tensile strength and the impact strength of the plastic box are further enhanced.
In a second aspect, the application provides a preparation method of an anti-aging plastic box, which adopts the following technical scheme: a preparation method of an anti-aging plastic box comprises the following steps:
s1, uniformly mixing modified starch, polypropylene, PE (polyethylene) wax, cellulose fibers, an antioxidant and an anti-aging agent to obtain a mixture;
s2, extruding the mixture prepared in the step S1 at 190-230 ℃, and performing injection molding to obtain the material.
By adopting the technical scheme, the mixture is extruded at 190-230 ℃, so that the components in the mixture are more compatible, the mixture is fed to a nozzle to just reach the required fluidity and viscosity, and the performance of the anti-aging plastic box obtained after extrusion molding is improved.
Preferably, the modified starch in step S1 is prepared by a method comprising the following steps:
(1) uniformly stirring starch, glycerol and sodium hexametaphosphate;
(2) plasticizing, extruding, cooling and granulating.
By adopting the technical scheme, the sodium hexametaphosphate modifies the starch, the sodium hexametaphosphate reacts with starch macromolecules to form a cross-linked network structure, and the strength of covalent cross-linking is far greater than that of a hydrogen bond, so that the tensile strength and the impact strength of the plastic box are improved.
In summary, the present application has the following beneficial effects:
1. the utility model provides a plastic box of ageing resistance has strengthened the ageing resistance of the plastic box of ageing resistance through adding antioxidant and anti-aging agent, and the antioxidant comprises main antioxidant and supplementary antioxidant two parts, and complementary mutually strengthens the tensile strength and the impact strength of the plastic box of ageing resistance jointly, and then further strengthens the ageing resistance of the plastic box of ageing resistance.
2. The plasticizer is added into the anti-aging plastic box, so that the toughness and the processability of the product can be enhanced.
Detailed Description
The present application will be described in further detail with reference to examples.
The utility model provides a plastic box of ageing resistance includes four sides and a bottom surface, and four sides splice into the plastic box of an uncovered setting with a bottom surface jointly.
The anti-aging plastic box of the present application has a large variety of cellulose fibers, and in the present embodiment, the cellulose fibers are preferably wood fibers or hemp fibers.
Preferably, the wood fiber is modified by the following method: dissolving the coupling agent in absolute ethyl alcohol to prepare a solution with the mass concentration of 2%, adding wood fiber in a water bath at the temperature of 60-70 ℃, uniformly stirring for 3-5h, and vacuum drying for 10-12h to obtain the wood fiber. Preferably, the coupling agent is a titanate coupling agent, preferably, the titanate coupling agent is isopropyl tri (dioctyl phosphate acyloxy) titanate, preferably, the wood fiber is 200 meshes, preferably, the stirring time is 4 hours, the vacuum drying is 11 hours, and the water bath temperature is 65 ℃.
Preferably, the modified starch is modified by the following method: taking a certain mass of starch, adding 35% of glycerol, then adding 6% of sodium hexametaphosphate, uniformly stirring by a high-speed stirrer, plasticizing and extruding by a double-screw extruder at the stirring temperature of 116 ℃ and the rotating speed of 150r/min, and cooling and granulating after extruding.
Preferably, the relative molecular mass of the polypropylene is 150000-200000 and less than 5 shorter branches are present per 1000 carbon atoms in the polypropylene backbone, and further preferably, the weight average molecular weight of the polypropylene is 150000-200000.
Preferably, the preparation method of the anti-aging plastic box comprises the following steps:
s1, placing the modified starch, the polypropylene, the PE wax, the fiber, the antioxidant and the anti-aging agent into a stirrer according to the proportion, and stirring at the stirring speed of 200r/min for 1h to obtain a mixture;
s2, placing the mixture prepared in the step S1 into a charging barrel of an injection molding machine, wherein the front temperature of the charging barrel is 219-230 ℃, the middle temperature of the charging barrel is 200-209 ℃, the rear temperature of the charging barrel is 190-199 ℃, extruding by using a screw at the rotating speed of 70-90r/min, and finally obtaining the anti-aging plastic box through injection molding of a mold, wherein the injection molding pressure is 50-70 MPa.
Wherein the front temperature of the charging barrel in the step S2 is 220 ℃, the middle temperature is 205 ℃, the rear temperature is 195 ℃, the screw rotation speed is 85r/min, and the injection molding pressure is 65 Mpa.
Preferably, the isocyanate is a polymeric MDI isocyanate, wherein the polymeric MDI isocyanate is polymeric methylene diphenyl diisocyanate.
Preferably, the epoxidized fatty acid butyl ester is octyl 3-octyloxirane octanoate.
TABLE 1 raw materials and manufacturers
Figure BDA0003089797890000041
Figure BDA0003089797890000051
Examples
Example 1
The anti-aging plastic box is prepared from the following raw materials in parts by weight: 10kg of modified starch, 70kg of polypropylene, 1kg of PE wax, 10kg of cellulose fiber, 5kg of antioxidant and 3kg of anti-aging agent. The cellulose fiber is a wood fiber, the antioxidant is composed of a main antioxidant and an auxiliary antioxidant according to the mass ratio of 3:2, the main antioxidant is composed of 2, 6-di-tert-butyl-4-hydroxymethyl phenol and isocyanate according to the mass ratio of 1:1, the auxiliary antioxidant is composed of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and N, N' -1, 4-phenylene dimaleimide according to the mass ratio of 1:1, and the anti-aging agent is composed of didodecyl thiodipropionate and zinc diethyldithiocarbamate according to the mass ratio of 1: 1.
The method for modifying modified starch of the embodiment comprises the following steps: taking starch, adding glycerol accounting for 35% of the mass of the starch, then adding sodium hexametaphosphate accounting for 6% of the mass of the starch, uniformly stirring by a high-speed stirrer, plasticizing and extruding by a double-screw extruder at the stirring temperature of 116 ℃ and the rotating speed of 150r/min, and cooling and granulating after extruding.
The preparation method of the anti-aging plastic box comprises the following steps:
s1, placing modified starch, polypropylene, PE wax, cellulose fiber, an antioxidant and an anti-aging agent into a stirrer according to the proportion, and stirring at a stirring speed of 200r/min for 1h to obtain a mixture;
s2, placing the mixture prepared in the step S1 into a charging barrel of an injection molding machine, wherein the front temperature of the charging barrel is 220 ℃, the middle temperature of the charging barrel is 205 ℃, the rear temperature of the charging barrel is 195 ℃, extruding the mixture by using a screw at the rotating speed of 85r/min, and finally performing one-step injection molding through a mold to obtain the anti-aging plastic box, wherein the injection molding pressure is 65 Mpa.
Examples 2 to 7
The anti-aging plastic boxes of the present examples 2 to 7 respectively provided different raw material component ratios, wherein the raw material component ratio of the anti-aging plastic box of each example is shown in table 2, and the unit of the raw material ratio is kg.
TABLE 2 examples 1-7 raw material ratios
Serial number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Modified starch 10 20 15 15 15 15 15
Polypropylene 70 80 75 75 75 75 75
PE wax 1 5 3 3 3 3 3
Cellulose fiber 10 15 13 13 13 13 13
Antioxidant agent 5 5 5 10 7 7 7
Anti-aging agent 3 3 3 3 3 5 4
Examples 2-7 differ from example 1 in that: the anti-aging plastic box is different in raw material ratio of each component, and the rest is the same as that in the embodiment 1.
Example 8
The anti-aging plastic box is prepared from the following raw materials in parts by weight: 15kg of modified starch, 75kg of polypropylene, 3kg of PE wax, 13kg of cellulose fiber, 7kg of antioxidant, 4kg of anti-aging agent and 1.5kg of plasticizer. The cellulose fiber is a wood fiber, the antioxidant is composed of a main antioxidant and an auxiliary oxidant according to a mass ratio of 3:2, the main antioxidant is composed of 2, 6-di-tert-butyl-4-hydroxymethyl phenol and isocyanate according to a mass ratio of 1:1, the auxiliary antioxidant is composed of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and N, N' -1, 4-phenylene bismaleimide according to a mass ratio of 1:1, the anti-aging agent is composed of didodecyl thiodipropionate and zinc diethyldithiocarbamate according to a mass ratio of 1:1, and the plasticizer is composed of tributyl citrate and octyl 3-octyloxirane octylate according to a mass ratio of 1: 1.
The modified starch of this example was modified in the same manner as in example 7.
The preparation method of the anti-aging plastic box of the embodiment comprises the following steps: the method comprises the following steps:
s1, placing modified starch, polypropylene, PE wax, cellulose fiber, an antioxidant, an anti-aging agent and a plasticizer into a stirrer according to the proportion, and stirring at the stirring speed of 200r/min for 1h to prepare a mixture;
s2, placing the mixture prepared in the step S1 into a charging barrel of an injection molding machine, wherein the front temperature of the charging barrel is 220 ℃, the middle temperature of the charging barrel is 205 ℃, the rear temperature of the charging barrel is 195 ℃, extruding the mixture by using a screw at the rotating speed of 85r/min, and finally performing one-step injection molding through a mold to obtain the anti-aging plastic box, wherein the injection molding pressure is 65 Mpa.
Example 9
This example is different from example 8 in that the aging inhibitor was composed of didodecyl thiodipropionate, zinc diethyldithiocarbamate and N, N-diacetylthiodipropionyl dihydrazide in a mass ratio of 2:3: 5. The rest is exactly the same as in example 8.
Example 10
This example is different from example 8 in that an age resistor was composed of didodecyl thiodipropionate, zinc diethyldithiocarbamate and N, N-diacetylthiodipropionyl dihydrazide in a mass ratio of 5:8: 9. The rest is exactly the same as in example 8.
Example 11
This example is different from example 10 in that the primary antioxidant is composed of 2, 6-di-t-butyl-4-hydroxymethylphenol, isocyanate, N '- (p-phenylene) bismaleimide in a mass ratio of 3:4:6, and the secondary antioxidant is composed of bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate, N' -1, 4-phenylenedimaleimide, bis (octadecyl) pentaerythritol diphosphite in a mass ratio of 2:3: 5. The rest is exactly the same as in example 10.
Example 12
This example is different from example 10 in that the primary antioxidant is composed of 2, 6-di-t-butyl-4-hydroxymethylphenol, isocyanate, N '- (p-phenylene) bismaleimide in a mass ratio of 5:8:9, and the secondary antioxidant is composed of bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate, N' -1, 4-phenylenedimaleimide, bis (octadecyl) pentaerythritol diphosphite in a mass ratio of 3:5: 7. The rest is exactly the same as in example 10.
Example 13
This example differs from example 12 in that the cellulose fibers are hemp fibers. The rest is exactly the same as in example 12.
Example 14
This example differs from example 12 in that the cellulose fibers are wood fibers modified with a coupling agent. The modification method of the wood fiber comprises the following steps: dissolving isopropyl tri (dioctyl phosphate acyloxy) titanate in absolute ethyl alcohol to prepare a solution with the mass concentration of 2%, adding wood fiber into a water bath at 65 ℃, uniformly stirring for 4h, and vacuum drying for 11h to obtain the cellulose acetate. The rest is exactly the same as in example 12.
Example 15
This example is different from example 14 in that the weight-average molecular weight of polypropylene is 50000-70000. The rest is exactly the same as in example 14.
Example 16
The difference between the embodiment and the embodiment 14 is that the plasticizer consists of trioctyl trimellitate, tributyl citrate and octyl 3-octyloxirane octoate in a mass ratio of 1:1:1, and the rest is completely the same as the embodiment 14.
Example 17
The difference between the embodiment and the embodiment 16 is that the preparation method of the anti-aging plastic box of the embodiment comprises the following steps: s1, placing modified starch, polypropylene, PE wax, cellulose fiber, an antioxidant and an anti-aging agent into a stirrer according to the proportion, and stirring at a stirring speed of 200r/min for 1h to obtain a mixture;
s2, placing the mixture prepared in the step S1 into a charging barrel of an injection molding machine, extruding the mixture by using a screw at the temperature of 220 ℃ and at the rotating speed of 85r/min, and finally performing one-step injection molding through a mold to obtain the anti-aging plastic box, wherein the injection molding pressure is 65 Mpa.
The rest is exactly the same as in example 16.
Example 18
The difference between the present example and example 8 is that the modified starch is sodium hexametaphosphate modified starch, wherein the modification method of the modified starch is as follows: heating starch with a certain mass at a water bath temperature of 45 ℃, simultaneously adding sodium sulfate which is 10% of the mass of the starch and serves as a stabilizer, continuously stirring, adding a sodium hydroxide solution to adjust the pH value to 10, then adding sodium hexametaphosphate which is 0.5% of the mass of the starch, reacting for 2 hours, adjusting the pH value to 6.3 by using a hydrochloric acid standard solution, filtering and washing for three times, then placing a sample in a drying oven with a temperature of 50 ℃, drying, crushing, sieving and then using. The rest is exactly the same as in example 8.
Comparative example
The anti-aging plastic box of the comparative example is prepared from the following raw materials in parts by weight: 15kg of starch, 75kg of polypropylene, 3kg of PE wax, 13kg of fibrilia, 8kg of isocyanate and the weight-average molecular weight of the polypropylene is 50000-70000.
The preparation method of the anti-aging plastic case of this comparative example was the same as that of example 1.
Performance test
And (3) testing tensile strength: the anti-aging plastic cases obtained in examples 1 to 18 and comparative example were subjected to tensile strength test according to the test method in ISO 527-2 "method for measuring tensile Properties of plastics", and the test results are shown in tables 3 and 4.
And (3) testing impact strength: the anti-aging plastic boxes prepared in examples 1 to 18 and comparative example 1 were subjected to impact strength test according to the test method in GB/T1843-2008/ISO 180:2000 "determination of Plastic Izod impact Strength", and the test results are shown in tables 3 and 4.
Thermal oxygen aging test: the anti-aging plastic boxes prepared in examples 1 to 18 and comparative example 1 were subjected to an artificial accelerated aging test according to the test method in GB/T7141-2008 "Plastic thermal aging test method", wherein the aging temperature was 90 ℃ and the aging time was 500 hours, and the test results are shown in Table 4.
TABLE 3 Performance test before Artificial accelerated ageing
Experiment grouping Tensile strength/MPa Impact Strength/KJ/m2
Example 1 18 6.6
Example 2 18.54 6.88
Example 3 19.08 7.16
Example 4 19.42 7.31
Example 5 19.76 7.46
Example 6 20.1 7.61
Example 7 20.94 7.76
Example 8 21.28 7.86
Example 9 21.62 7.96
Example 10 21.96 8.06
Example 11 22.3 8.16
Example 12 22.64 8.26
Example 13 22.13 8.58
Example 14 23.63 8.71
Example 15 22.73 8.65
Example 16 24.8 8.82
Example 17 22.06 7.97
Example 18 20.45 7.23
Comparative example 15 5.3
TABLE 4 Performance test after artificially accelerated aging
Figure BDA0003089797890000091
Figure BDA0003089797890000101
By combining the example 1 and the comparative example and combining the tables 3 and 4, the tensile strength and the impact strength of the anti-aging plastic box are reduced by adding the antioxidant and the anti-aging agent into the raw materials of the anti-aging plastic box under the compounding action of the anti-aging agent and the antioxidant, but the reduction range is small, and meanwhile, the mass change rate of the anti-aging plastic box is small before and after manual accelerated aging.
In combination with examples 1-12 and tables 3 and 4, it can be seen that the addition of the plasticizer can enhance the processability of the anti-aging plastic case, and simultaneously, the addition of the plasticizer can be synergistic by the combination of the primary antioxidants and the secondary antioxidants, and the tensile strength and impact strength of the anti-aging plastic case can be kept better.
By combining examples 12-16 and tables 3 and 4, it can be seen that the compatibility between the plastic and the wood fiber is increased after the wood fiber is modified by the titanate coupling agent, and the tensile strength and the impact strength of the anti-aging plastic box can be kept better by using the high-density polypropylene as the polypropylene, and the difference of the mass change rate of the anti-aging plastic box is small after artificial aging acceleration.
By combining examples 16-17, and by combining tables 3 and 4, it can be seen that by subjecting the mixture from which the anti-aging plastic box was prepared to three temperature stages in sequence in an injection molding machine, the overall performance of the prepared anti-aging plastic box was superior to that of the anti-aging plastic box subjected to only one temperature.

Claims (6)

1. An anti-aging plastic box is characterized in that: the material is mainly prepared from the following raw materials in parts by weight: 10-20 parts of modified starch, 70-80 parts of polypropylene, 1-5 parts of PE (polyethylene) wax, 10-15 parts of cellulose fiber, 5-10 parts of antioxidant and 3-5 parts of anti-aging agent, wherein the antioxidant consists of a main antioxidant and an auxiliary antioxidant in a mass ratio of (2-3) to (1-2), and the modified starch is sodium hexametaphosphate modified starch; the anti-aging agent consists of didodecyl thiodipropionate, zinc diethyldithiocarbamate and N, N-diacetyl thiodipropionyl dihydrazide according to the mass ratio of (2-5) to (3-8) to (5-9); the main antioxidant consists of 2, 6-di-tert-butyl-4-hydroxymethyl phenol, isocyanate and N, N '- (p-phenylene) bismaleimide according to the mass ratio of (3-5) to (4-8) to (6-9), and the auxiliary antioxidant consists of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, N' -1, 4-phenylene bismaleimide and bis (octadecyl) pentaerythritol diphosphite according to the mass ratio of (2-3) to (3-5) to (5-7).
2. The anti-aging plastic box according to claim 1, characterized in that: the cellulose fiber is obtained by treating wood fiber with a titanate coupling agent.
3. The anti-aging plastic box according to claim 2, characterized in that: the relative molecular mass of the polypropylene is 150000-.
4. The anti-aging plastic box according to claim 3, wherein: the raw materials also comprise 1-3 parts by weight of plasticizer, and the plasticizer is at least two of trioctyl trimellitate, tributyl citrate and epoxy fatty acid butyl ester.
5. A method of making the anti-aging plastic case of claim 1, wherein: the method comprises the following steps:
s1, uniformly mixing modified starch, polypropylene, PE (polyethylene) wax, cellulose fibers, an antioxidant and an anti-aging agent to obtain a mixture;
s2, extruding the mixture prepared in the step S1 at 190-230 ℃, and performing injection molding to obtain the material.
6. The method for preparing an anti-aging plastic box according to claim 5, characterized in that: the modified starch in the step S1 is prepared by a method comprising the following steps:
(1) uniformly stirring starch, glycerol and sodium hexametaphosphate;
(2) plasticizing, extruding, cooling and granulating.
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