CN112980208B - Bio-based straw composite material and preparation method and application thereof - Google Patents

Bio-based straw composite material and preparation method and application thereof Download PDF

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CN112980208B
CN112980208B CN202110413015.0A CN202110413015A CN112980208B CN 112980208 B CN112980208 B CN 112980208B CN 202110413015 A CN202110413015 A CN 202110413015A CN 112980208 B CN112980208 B CN 112980208B
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CN112980208A (en
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姜海峰
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Haiyun Industrial Shanghai Co ltd
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A23G9/44—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor characterised by shape, structure or physical form
    • A23G9/50—Products with edible or inedible supports, e.g. cornets
    • A23G9/503—Products with edible or inedible supports, e.g. cornets products with an inedible support, e.g. a stick
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract

The application relates to the field of bio-based composite materials, and particularly discloses a bio-based straw composite material and a preparation method and application thereof. The bio-based straw composite material comprises the following components in parts by weight: 35-55 parts of wheat straw fiber, 45-65 parts of polypropylene, 1-3 parts of compatilizer and 6-12 parts of nano tough material; the preparation method comprises the following steps: crushing polypropylene, sieving with a 120-mesh sieve, mixing with wheat straw fiber, drying at 80-85 ℃ for 2h, adding a compatilizer and a nano toughening material, mixing at 40-60 ℃ for 15-20min, extruding, bracing, cold cutting, granulating, and drying to obtain the bio-based straw composite material. The bio-based straw composite material can be used for preparing ice cream sticks, household daily necessities, tableware and wood-like products, and has the advantages of high compatibility of straw and plastic, good mechanical property and mildew and bacteria corrosion prevention of the ice cream sticks.

Description

Bio-based straw composite material and preparation method and application thereof
Technical Field
The application relates to the technical field of bio-based composite materials, in particular to a bio-based straw composite material and a preparation method and application thereof.
Background
The straw is a gramineous plant, is the most main agricultural byproduct in the world and is also an agricultural product with the highest utilization value, but for a long time, the crop straw is mainly used for fertilizers, dyes, feeds and papermaking raw materials, the utilization rate is low, and most of the rest straws are incinerated to cause serious haze or other air pollution. One of the utilization directions of the straws is to develop straw-plastic products to replace wood-plastic materials so as to reduce the deforestation amount, reduce the threat of the rapid development of the wood-plastic industry to the forest and obtain the benefit of environmental protection while fully utilizing the straw resources.
The main components of the straw are cellulose, hemicellulose and lignin, when the straw and plastic are compounded into the bio-based composite material, the straw and the plastic have the problem of difficult compatibility due to the fact that the density of the straw is low, the weight is light, the bulk density after crushing is only 0.06-0.1g/cm3 which is far lower than that of the plastic, and the straw and the plastic are easy to float and agglomerate and cannot be mixed uniformly.
In view of the above-mentioned related technologies, the inventors believe that the straw and the plastic are difficult to be compatible when the bio-based straw composite material is prepared, and compared with the traditional plastic, the mechanical properties of the bio-based straw composite material still need to be improved.
Disclosure of Invention
In order to improve the compatibility of straws and plastics and improve the mechanical property of a bio-based straw composite material, the application provides a bio-based straw composite material and a preparation method and application thereof.
In a first aspect, the application provides a bio-based straw composite material, which adopts the following technical scheme:
a bio-based straw composite material comprises the following components in parts by weight: 35-55 parts of wheat straw fiber, 45-65 parts of polypropylene, 1-3 parts of compatilizer and 6-12 parts of nano tough material;
the preparation method of the wheat straw fiber comprises the following steps: (1) crushing and drying wheat straws to form wheat straw fibers, mixing 1-2 parts by weight of titanate coupling agent, 0.4-0.8 part by weight of maleic anhydride grafted polypropylene wax and 5-10 parts by weight of absolute ethyl alcohol to form spraying liquid, uniformly spraying the spraying liquid on the wheat straw fibers, and carrying out microwave radiation for 3-5min under the power of 800-900W, wherein the mass ratio of the wheat straw fibers to the spraying liquid is 1: 0.5-0.8; (2) and (2) placing the wheat straw fiber treated in the step (1) into a xylitol enzyme solution with the concentration of 60-80%, soaking for 3-5h at 50-80 ℃, washing, and drying in vacuum, wherein the mass ratio of the wheat straw fiber to the xylitol enzyme solution is 1: 1.3-1.5.
By adopting the technical scheme, as the titanate coupling agent and the maleic anhydride grafted polypropylene wax are dissolved in ethanol as spraying liquid and sprayed on the wheat straw fiber, under the action of microwave, the roughness of the surface of the wheat straw fiber is increased, the polarity is reduced, the hydroxyl on the surface of the straw, the titanate coupling agent and the maleic anhydride grafted polypropylene wax are subjected to esterification reaction, the polarity of the wheat straw fiber is weakened, the affinity of the wheat straw fiber and polypropylene is improved, the wheat straw fiber is more favorably wrapped by the polypropylene, an interface layer with good bonding strength is formed, and then, carrying out impregnation treatment by using xylitol enzyme, so that the content of hydroxyl in the wheat straws is reduced, hemicellulose and free cellulose existing in the straw fibers are reduced, the compatibility of the straw fibers and polypropylene treatment is improved, the straw fibers and the polypropylene are combined more tightly, and the mechanical property is improved.
Preferably, each part by weight of the nano tough material comprises the following components in parts by weight: 4.5-6 parts of nano zinc oxide, 2-3 parts of EPDM (ethylene-propylene-diene monomer), 10-14 parts of PMMA (polymethyl methacrylate), 3.4-5.2 parts of carbon fiber, 1.6-2.8 parts of glass fiber, 0.3-0.6 part of dispersing agent, 0.4-0.8 part of adhesive and 5-10 parts of silica sol.
By adopting the technical scheme, the carbon fiber has the defects of high strength and high hardness but larger rigidity, and the glass fiber has high mechanical strength but is more brittle, so that the rigidity and brittleness of the glass fiber and the carbon fiber are improved by using the silica gel, so that the glass fiber and the carbon fiber have better strength, tensile resistance and improved toughness; the nano zinc oxide has extremely fine particles and high surface activity, and can improve the impact strength and tensile strength of the nano toughening material; PMMA has higher surface hardness and weather resistance, EDPM is nonpolar rubber, has excellent hydrophobicity, and can reduce the hydrophilicity of the composite material; the compatibility of the bio-based straw composite material can be improved, the interface binding force is improved, and the mechanical property is enhanced under the coordination effect of various raw materials.
Preferably, the preparation method of the nano toughening material comprises the following steps: (1) uniformly mixing carbon fibers and glass fibers, adding the mixture into silica sol, uniformly mixing under the pressure of- (0.5-1) MPa, drying, and crushing to form a framework material A;
(2) adding nano zinc oxide into 40-50% adhesive solution prepared by mixing adhesive and water, uniformly mixing, uniformly spraying the mixture on EPDM, and vacuum drying to form a framework material B;
(3) mixing the framework material A, the framework material B, the dispersing agent and the PMMA, heating to 130-140 ℃, uniformly mixing, drying at 60-80 ℃ for 4-6h, and crushing to prepare the nano toughening material.
By adopting the technical scheme, firstly, the composite power of the silica sol, the carbon fiber and the inner pores of the glass fiber is increased by adopting a vacuum impregnation and pressurization mode, and simultaneously, the air bubbles in the carbon fiber and the glass fiber are completely discharged, so that more silica sol is injected into the pores of the fiber matrix, and the tensile resistance of the fiber matrix is improved; the nano zinc oxide is adhered to the surface of the EPDM by using an adhesive, the nano zinc oxide plays a bridging role between adjacent EDPMs, a stress field around the nano zinc oxide and a stress field around the EPDM are mutually overlapped, the distance between particles is greatly reduced, so that the framework material B is subjected to brittle-tough transition, the impact strength is remarkably improved, and the nano zinc oxide and the EPDM can be prevented from being agglomerated by adopting a spraying and adhering mode; and finally, coating PMMA on the framework material A and the framework material B, enhancing the interface interaction force between the nano zinc oxide, the silicon dioxide and the polypropylene, promoting the dispersion of the nano zinc oxide and the silicon dioxide in the polypropylene, improving the maximum stress of crack formation of the bio-based composite material, prolonging the crack initiation time, and enhancing the capability required by crack initiation and expansion, thereby improving the tensile strength and the impact strength of the bio-based composite material.
Preferably, the dispersant is one or a combination of several of nonylphenol polyoxyethylene ether, sulfonate copolymer and polyacrylamide.
By adopting the technical scheme, the dispersion of the framework material A and the framework material B in PMM can be effectively improved by using the nonylphenol polyoxyethylene ether, the sulfonate copolymer and the polyacrylamide as the dispersing agents, the wetting ability and the stabilizing effect on silicon dioxide in the framework material A are realized, the interfacial tension of a system is reduced, and the framework material A and the framework material B are rapidly dispersed under the action of mechanical external force.
Preferably, the compatilizer is maleic anhydride grafted polylactic acid and KH550 silane coupling agent in a mass ratio of 1: 0.6-0.9.
By adopting the technical scheme, the maleic anhydride functional group in the maleic anhydride grafted polylactic acid and the hydroxyl on the surface of the straw fiber are subjected to esterification reaction to form a hydrogen bond, and the nonpolar molecular bond in the maleic anhydride grafted polylactic acid can be intertwined with a polypropylene molecular chain to play a role of a bridge, so that the interface bonding force between the straw fiber and the polypropylene is increased, and the mechanical property of the composite material is improved; the KH550 silane coupling agent is combined on the surface of the straw fiber by a silicon-oxygen bond to form a stable structure, and the hydrophilicity of the fiber is reduced, so that the interfacial adhesion between the straw fiber and polypropylene is greatly improved, and the compatibility between the straw fiber and a polypropylene matrix is good; meanwhile, the maleic anhydride grafted polylactic acid and the KH550 silane coupling agent are used as compatilizers, so that the polarity of the straw fiber can be effectively reduced, the bonding strength between the straw fiber and polypropylene is increased, and the mechanical property is enhanced.
In a second aspect, the application provides a preparation method of a bio-based straw composite material, which adopts the following technical scheme: a preparation method of a bio-based straw composite material comprises the following steps:
crushing polypropylene, sieving with a 120-mesh sieve, mixing with wheat straw fiber, drying at 80-85 ℃ for 2h, adding a compatilizer and a nano toughening material, uniformly mixing, extruding at 140-190 ℃ to obtain a melt, and bracing, cold cutting and granulating the melt to obtain the bio-based straw composite material.
By adopting the technical scheme, the polypropylene and the wheat straw fiber are mixed and then dried, the internal moisture is removed, then the compatilizer and the nano toughening material are mixed, extruded, cooled and granulated, the preparation method is simple, and the industrial operation is easy.
In a third aspect, the application provides an application of a bio-based straw composite material, which adopts the following technical scheme: an application of bio-based straw composite material in preparing ice cream sticks, household daily necessities, tableware and wood-like products.
By adopting the technical scheme, the wheat straw fiber and the polypropylene are used for preparing ice cream sticks, furniture daily necessities, tableware and wood-like products, so that the ice cream sticks, the furniture daily necessities, the tableware and the wood-like products have the advantages of greenness, naturalness, low carbon, environmental protection and energy conservation, have natural plant textures on the surfaces, and are widely used and safe to use.
Preferably, the preparation method of the ice cream stick comprises the following steps: adding the melt or the bio-based straw composite material into a mold, maintaining the pressure for 0.5-1.5min at 1.8-2.2MPa, and naturally cooling to obtain the ice cream stick, wherein the bio-based straw composite material is heated to 140-160 ℃ before being added into the mold.
By adopting the technical scheme, the bio-based straw composite material is added into the mould after being melted, or the melt is directly added into the mould, so that the ice cream stick can be manufactured, and has good strength and hardness, is not easy to deform and is environment-friendly.
Preferably, when the ice cream stick is cooled to room temperature, the ice cream stick is placed into a sodium hydroxide solution with the mass fraction of 5-7%, treated at 80-90 ℃ for 50-60min, washed to be neutral by deionized water, placed into a mildew-proof treatment liquid, maintained at the pressure of- (0.08-0.1) MPa for 1-2h, and dried at 45-50 ℃ for 1-2h, wherein the mass ratio of the ice cream stick to the mildew-proof treatment liquid is 1: 1.5-1.8.
By adopting the technical scheme, the ice cream stick is easy to be corroded by mould when stored, large-area mould spots can be generated on the surface of the ice cream stick after mould corrosion, the ice cream stick cannot be used continuously, the ice cream stick is treated by sodium hydroxide solution, so that the fibre on the surface of the ice cream stick is fibrillated, namely, the straw fibre bundle in the composite material is split into smaller fibres, the diameter of the fibres is reduced, the length-diameter ratio is increased, the contact area with a polypropylene material is increased, the polypropylene material is better combined, the mould-proof effect of the ice cream stick is improved, and finally, the mould-proof treatment liquid enters the interior of the ice cream stick through pressurization and impregnation, so that the mould-proof effect of the ice cream stick is improved.
Preferably, the mildew-proof treatment liquid is prepared from the following components in parts by weight: 0.8-1.3 parts of dill seed essential oil, 0.4-0.8 part of tea extract, 1-1.5 parts of litsea cubeba essential oil and 2-3 parts of distilled water.
By adopting the technical scheme, the essential oil of litsea cubeba contains citral as a main component, and has the effects of increasing total MDA and H202 in cells, increasing substance leakage in cells, and reducing the content of total lipid and ergosterol, so that mould is induced to generate serious membrane lipid peroxidation damage, the permeability of cell membranes is increased, the structure of the cell membranes is damaged, the function of inhibiting the growth of mould is achieved, and the broad-spectrum bacteriostasis is realized without toxicity; the tea extract contains tea polyphenol as main active component, has the effects of inhibiting cell proliferation and the like, and has strong inhibition capacity on various microorganisms; the dill seed essential oil has antimicrobial, antifungal and antibacterial properties, and has strong antibacterial and mildewproof effects when the litsea cubeba essential oil, the tea extract and the dill seed essential oil are used in a synergistic manner.
In summary, the present application has the following beneficial effects:
1. according to the method, the titanate coupling agent and the maleic anhydride grafted polypropylene wax are adopted to spray the wheat straw fibers, after microwave treatment is used, the roughness and the polarity of the wheat straw fibers are increased due to the microwaves, so that the titanate coupling agent and the maleic anhydride grafted polypropylene wax are grafted to the surfaces of the fibers, the mutual penetration depth and the mechanical interlocking of the interfaces are enhanced, the interface bonding force between the wheat straw fibers and the polypropylene is enhanced, finally, the wheat straw fibers are treated by the xylitol enzyme, the hydroxyl content in the wheat straw fibers is reduced, the compatibility between the wheat straw fibers and the polypropylene is increased, and the mechanical property of the bio-based straw composite material is improved.
2. In the application, a pressurizing and dipping mode is preferably adopted, so that silica gel enters pores of glass fibers and carbon fibers, the rigidity and the brittleness of the carbon fibers and the glass fibers are reduced, then nano zinc oxide is attached to the surface of EDPM through an adhesive, the hardness of the EDPM is increased, and finally PMMA is coated on the surfaces of the carbon fibers, the glass fibers and the nano zinc oxide, the interaction among components such as polypropylene, nano zinc oxide and carbon fibers is enhanced through the PMMA coated on the surface, so that the nano toughening material is dispersed in the bio-based straw composite material in a nano size, and the mechanical effect of the bio-based straw composite material is improved.
3. Preferably use maleic anhydride grafting polylactic acid and KH550 silane coupling agent as the compatilizer in this application, maleic anhydride grafting polylactic acid takes place esterification reaction with the surperficial hydroxyl of fibre, and KH550 silane coupling agent combines on the fibre surface with the silica bond, reduces straw fiber's hydrophilicity, increases the compatibility between straw and the polypropylene, increases the interfacial adhesion dynamics, improves mechanical strength.
4. The bio-based straw composite material is used for preparing ice cream sticks, wood-like products, household daily necessities and tableware, and has the advantages of being green, natural, low-carbon, environment-friendly and energy-saving.
5. The mildew-proof treatment liquid is used for treating the ice cream sticks, so that the ice cream sticks can be prevented from mildewing during storage, and the ice cream sticks can be prevented from being used continuously due to the large-area mildew spots.
Detailed Description
Preparation examples 1 to 7 of wheat straw fiber
The titanate coupling agent in preparation examples 1-7 is selected from Dongguan Yisheng chemical Co., Ltd, and the model is DC 2-A; the maleic anhydride grafted polypropylene wax is selected from Yuan Yucheng New materials, Inc. of Dongguan, model number PP 001; the xylitol enzyme is selected from Shanghai West Biotech limited.
Preparation example 1: (1) crushing wheat straws to 400 meshes, carrying out vacuum drying for 2 hours at 120 ℃ to form wheat straw fibers, mixing 1kg of titanate coupling agent, 0.4kg of maleic anhydride grafted polypropylene wax and 5kg of absolute ethyl alcohol to form spraying liquid, uniformly spraying the spraying liquid on the wheat straw fibers, and carrying out microwave radiation for 5 minutes at the power of 800W, wherein the mass ratio of the wheat straw fibers to the spraying liquid is 1: 0.5;
(2) and (2) placing the wheat straw fiber treated in the step (1) into a xylitol enzyme solution with the concentration of 60%, soaking for 5h at 50 ℃, washing for 3 times, and vacuum-drying for 2h at 80 ℃, wherein the mass ratio of the wheat straw fiber to the xylitol enzyme solution is 1: 1.3.
Preparation example 2: (1) crushing wheat straws to 400 meshes, carrying out vacuum drying for 3h at 110 ℃ to form wheat straw fibers, mixing 1.5kg of titanate coupling agent, 0.6kg of maleic anhydride grafted polypropylene wax and 8kg of absolute ethyl alcohol to form spraying liquid, uniformly spraying the spraying liquid on the wheat straw fibers, and carrying out microwave radiation for 4min at the power of 850W, wherein the mass ratio of the wheat straw fibers to the spraying liquid is 1: 0.6;
(2) and (2) putting the wheat straw fiber treated in the step (1) into a xylitol enzyme solution with the concentration of 70%, soaking for 4h at 70 ℃, washing for 3 times, and vacuum-drying for 1.5h at 80 ℃, wherein the mass ratio of the wheat straw fiber to the xylitol enzyme solution is 1: 1.4.
Preparation example 3: (1) crushing wheat straws to 400 meshes, carrying out vacuum drying for 1.5h at 115 ℃ to form wheat straw fibers, mixing 2kg of titanate coupling agent, 0.8kg of maleic anhydride grafted polypropylene wax and 10kg of absolute ethyl alcohol to form spraying liquid, uniformly spraying the spraying liquid on the wheat straw fibers, and carrying out microwave radiation for 3min at 900W, wherein the mass ratio of the wheat straw fibers to the spraying liquid is 1: 0.8;
(2) and (2) placing the wheat straw fiber treated in the step (1) into a xylitol enzyme solution with the concentration of 80%, soaking for 3h at 80 ℃, washing for 3 times, and vacuum-drying for 2h at 70 ℃, wherein the mass ratio of the wheat straw fiber to the xylitol enzyme solution is 1: 1.5.
Preparation example 4: the difference from the preparation example 1 is that no titanate coupling agent is added in the spraying liquid in the step (1).
Preparation example 5: the difference from preparation example 1 is that maleic anhydride grafted polypropylene wax was not added to the spray liquid in step (1).
Preparation example 6: the difference from preparation example 1 is that microwave irradiation was not performed in step (1).
Preparation example 7: the difference from preparation example 1 is that step (2) was not performed.
Preparation examples 1 to 6 of Nanomagnetic ductile Material
The nanometer zinc oxide in preparation examples 1-6 is selected from Ntech limited company of Yamei, Zhejiang, with fineness of 50 nm; the EPDM is selected from Shanghai Furun plasticizing science and technology Limited company, and the model is 3090 EM; PMMA is selected from Shanghai Hongyilai plastics Co., Ltd, and the model is VH 6001; the polyvinyl alcohol is selected from Qizhou plastication Co., Ltd, Dongguan city, and the model is BP-17; the carboxymethyl cellulose is selected from Ningpo republic of chemical industry Co., Ltd, and the model is jy-004; the starch is selected from Shandong Furan chemical science and technology limited, with a model of 0123; the sulfonate copolymer is selected from Kaiyn chemical engineering of Shanghai, and has model number of DH-5038; the polyoxyethylene nonyl phenyl ether is selected from Guangzhou Shi chemical Co., Ltd, and has model number NP 8.6; the polyacrylamide is selected from Jinquan chemical Co., Ltd, Ningchun, with the model number of JQ-002, carbon fiber Shanghaihongshuo composite material science and technology Co., Ltd, with the product number of 05; the glass fiber is selected from Xinshengjia composite material, Inc. of Dongguan city, and the product number is XSJ-40; the silica sol is selected from Shanghai Silicarb materials science and technology, Inc. model number NSHC-520.
Preparation example 1: (1) uniformly mixing 3.4kg of carbon fiber and 1.6kg of glass fiber, adding the mixture into 5kg of silica sol, uniformly mixing under-0.5 MPa, and drying at 70 ℃ for 2 hours to form a framework material A;
(2) adding 4.5kg of nano zinc oxide into 40% adhesive solution prepared by mixing 0.4kg of adhesive and water, uniformly mixing, uniformly spraying the mixture on 2kg of EPDM, and drying in vacuum at 80 ℃ for 2h to form a framework material B, wherein the adhesive is polyvinyl alcohol;
(3) mixing the framework material A, the framework material B, 0.3kg of dispersing agent and 10kg of PMMA, heating to 130 ℃, uniformly mixing, drying at 60 ℃ for 6 hours, and crushing to 20nm to prepare the nano toughening material, wherein the dispersing agent is nonylphenol polyoxyethylene ether.
Preparation example 2: (1) uniformly mixing 4.3kg of carbon fiber and 2.2kg of glass fiber, adding the mixture into 8kg of silica sol, uniformly mixing under-0.8 MPa, and drying for 1h at the temperature of 80 ℃ to form a framework material A;
(2) adding 5.3kg of nano zinc oxide into 45% adhesive solution prepared by mixing 0.6kg of adhesive and water, uniformly mixing, uniformly spraying the mixture on 2.5kg of EPDM, and drying in vacuum at 85 ℃ for 1.5h to form a framework material B, wherein the adhesive is carboxymethyl cellulose;
(3) mixing the framework material A, the framework material B, 0.5kg of dispersant and 12kg of PMMA, heating to 135 ℃, uniformly mixing, drying at 70 ℃ for 5 hours, and crushing to 30nm to prepare the nano toughening material, wherein the dispersant is sulfonate copolymer.
Preparation example 3: (1) uniformly mixing 5.2kg of carbon fiber and 2.8kg of glass fiber, adding the mixture into 10kg of silica sol, uniformly mixing under-1 MPa, drying at 75 ℃ for 1.5h, and crushing to form a framework material A;
(2) adding 6kg of nano zinc oxide into 50% adhesive solution prepared by mixing 0.8kg of adhesive and water, uniformly mixing, uniformly spraying the mixture on 3kg of EPDM, and drying the mixture in vacuum at 90 ℃ for 1 hour to form a framework material B, wherein the adhesive is starch;
(3) mixing the framework material A, the framework material B, 0.6kg of dispersing agent and 14kg of PMMA, heating to 140 ℃, uniformly mixing, drying at 80 ℃ for 4 hours, and crushing to 40nm to prepare the nano toughening material, wherein the dispersing agent is polyacrylamide.
Preparation example 4: (1) adding 6kg of nano zinc oxide into 50% adhesive solution prepared by mixing 0.8kg of adhesive and water, uniformly mixing, uniformly spraying the mixture on 3kg of EPDM, drying the mixture in vacuum at 90 ℃ for 1 hour, and crushing to form a framework material B, wherein the adhesive is starch;
(2) mixing the framework material B, 0.6kg of dispersant and 14kg of PMMA, heating to 130 ℃, uniformly mixing, drying at 80 ℃ for 4 hours, and crushing to 40nm to prepare the nano toughening material, wherein the dispersant is polyacrylamide.
Preparation example 5: (1) uniformly mixing 5.2kg of carbon fiber and 2.8kg of glass fiber, adding the mixture into 10kg of silica sol, uniformly mixing the mixture under the pressure of-1 MPa, drying the mixture for 2 hours at the temperature of 70 ℃, and crushing the mixture to form a framework material A;
(2) mixing the framework material A, 0.6kg of dispersant and 14kg of PMMA, heating to 130 ℃, uniformly mixing, drying at 80 ℃ for 4 hours, and crushing to 40nm to prepare the nano toughening material, wherein the dispersant is polyacrylamide.
Preparation example 6: the difference from preparation example 1 is that step (3) is: uniformly mixing the framework material A, the framework material B and 0.6kg of dispersant, drying for 4 hours at 80 ℃, and crushing to 40nm to prepare the nano toughening material, wherein the dispersant is polyacrylamide.
Examples
In the following examples, the polypropylene is selected from Yunlong plastification import and export Co., Ltd, Suzhou, model No. R307Y, the performance parameters of which are shown in Table 1, the nano-silica is selected from New materials Co., Ltd, Nanjing Baokite, model No. PTA, and the PE is selected from Yijia source New materials Co., Ltd, Suzhou, with a product No. 6102; the maleic anhydride grafted polylactic acid is selected from Shenzhen Xinyi plastic chemical company Limited with the model of xy1093, and the KH550 silane coupling agent is selected from Henan Zhenya chemical product Limited.
TABLE 1 Property parameters of polypropylene type R307Y
Figure BDA0003024838210000071
Figure BDA0003024838210000081
Example 1: the raw material formulation of the bio-based straw composite material is shown in table 2, and the preparation method of the bio-based straw composite material comprises the following steps:
crushing polypropylene, sieving the crushed polypropylene with a 120-mesh sieve, mixing the crushed polypropylene with wheat straw fibers, drying the mixture at 80 ℃ for 2 hours, adding a compatilizer and a nano toughening material, uniformly mixing the mixture, putting the mixture into a hot runner co-extrusion die for hot melt extrusion to obtain a melt, bracing, cold cutting and granulating the melt to obtain the bio-based straw composite material, wherein the temperature of a first area of the hot runner co-extrusion die is 185 ℃, the temperature of a second area is 165 ℃, the temperature of a third area is 140 ℃, the injection pressure of the first area, the second area and the third area is 35bar, the injection speed is 99%, the wheat straw fibers are prepared by the preparation example 1, the nano toughening material is nano silicon dioxide, and the compatilizer is polyethylene glycol.
TABLE 2 raw material ratios of bio-based straw composites in examples 1-5
Figure BDA0003024838210000082
Examples 2 to 5: a bio-based straw composite material is different from the embodiment 1 in that the raw material formula is shown in the table 1.
Example 6: a bio-based straw composite material is different from the embodiment 1 in that the preparation method comprises the following steps: crushing polypropylene, sieving the crushed polypropylene with a 120-mesh sieve, mixing the crushed polypropylene with wheat straw fibers, drying the mixture at 80 ℃ for 2 hours, adding a compatilizer and a nano toughening material, uniformly mixing the mixture, putting the mixture into a hot runner co-extrusion die for hot melt extrusion to obtain a melt, and bracing, cold cutting and granulating the melt to obtain the bio-based straw composite material, wherein the temperature of a first area of the hot runner co-extrusion die is 190 ℃, the temperature of a second area of the hot runner co-extrusion die is 170 ℃, and the temperature of a third area of the hot runner co-extrusion die is 145 ℃.
Example 7: a bio-based straw composite material, which is different from the embodiment 1 in that wheat straw fiber is prepared by the preparation example 2 of the wheat straw fiber.
Example 8: a bio-based straw composite material, which is different from the embodiment 1 in that wheat straw fiber is prepared by the preparation example 3 of the wheat straw fiber.
Example 9: a bio-based straw composite material is different from the embodiment 1 in that the nano toughening material is prepared from the preparation example 1 of the nano toughening material.
Example 10: a bio-based straw composite material is different from the embodiment 1 in that a nano toughening material is prepared from a preparation example 2 of the nano toughening material.
Example 11: a bio-based straw composite material, which is different from the embodiment 1 in that the nano toughening material is prepared by the preparation example 3 of the nano toughening material.
Example 12: a bio-based straw composite material is different from the embodiment 1 in that the nano toughening material is prepared by the preparation example 4 of the nano toughening material.
Example 13: a bio-based straw composite material, which is different from the embodiment 1 in that the nano toughening material is prepared by the preparation example 5 of the nano toughening material.
Example 14: a bio-based straw composite material is different from the embodiment 1 in that the nano toughening material is prepared from the preparation example 6 of the nano toughening material.
Example 15: a bio-based straw composite material is different from the embodiment 1 in that a compatilizer is maleic anhydride grafted polylactic acid and KH550 silane coupling agent in a mass ratio of 1: 0.6.
Example 16: a bio-based straw composite material is different from the embodiment 1 in that a compatilizer is maleic anhydride grafted polylactic acid and KH550 silane coupling agent in a mass ratio of 1: 0.7.
Example 17: a bio-based straw composite material is different from the embodiment 1 in that a compatilizer is maleic anhydride grafted polylactic acid and KH550 silane coupling agent in a mass ratio of 1: 0.9.
Example 18: a bio-based straw composite material, which is different from the embodiment 1 in that the compatilizer is maleic anhydride grafted polylactic acid.
Example 19: a bio-based straw composite material, which is different from the embodiment 1 in that a compatilizer KH550 silane coupling agent.
Example 20: a bio-based straw composite material is different from example 1 in that a nano toughening material is prepared from preparation example 1, and a compatilizer is maleic anhydride grafted polylactic acid and KH550 silane coupling agent in a mass ratio of 1: 0.6.
Comparative example
Comparative example 1: a bio-based straw composite material, which is different from the embodiment 1 in that wheat straw fiber is prepared by the preparation example 4 of the wheat straw fiber.
Comparative example 2: a bio-based straw composite material, which is different from the embodiment 1 in that wheat straw fiber is prepared by the preparation example 5 of the wheat straw fiber.
Comparative example 3: a bio-based straw composite material, which is different from example 1 in that wheat straw fiber is prepared from the preparation example 6 of wheat straw fiber.
Comparative example 4: a bio-based straw composite material, which is different from example 1 in that wheat straw fiber is prepared from the preparation example 7 of wheat straw fiber.
Comparative example 5: a bio-based straw composite material is different from that in example 1 in that wheat straw fiber is prepared by crushing to 400 meshes and drying at 120 ℃ for 2 hours.
Comparative example 6: a bio-based straw composite material, which is different from the embodiment 1 in that no compatilizer is added.
Comparative example 7: a bio-based straw composite material, which is different from the embodiment 1 in that no nano toughening material is added.
Comparative example 8: a preparation method of bio-based straw composite plastic comprises the following steps: (1) preparing 1 part of compatilizer into an ethanol solution, uniformly spraying the ethanol solution on a mixture containing 1 part of CNCs or CNFs and 40 parts of straws, standing at room temperature for 6 hours, drying at 105 ℃ for 2 hours, reserving the dried mixture, adding 47 parts of polyolefin, 8 parts of plasticizer, 2 parts of heat stabilizer and 1 part of internal lubricant, stirring and uniformly mixing at 60-150 ℃, wherein the compatilizer is PEG800, the polyolefin is PP, the plasticizer is sorbitol, the heat stabilizer is zinc stearate, and the internal lubricant is liquid paraffin; (2) reacting in a double-screw extruder: and (2) adding the material obtained in the step (1) into a double-screw extruder, mixing and granulating at the temperature of 130-.
Performance test
Bio-based straw composites were prepared according to the methods of examples 1-20 and comparative examples 1-8, and the mechanical properties of the composites were measured according to the following methods, and the results are reported in Table 3.
1. Tensile strength and elongation at break: testing according to ASTM D638/ISO 527, wherein the testing speed is 50 mm/min;
2. flexural strength and flexural modulus: testing according to ASTM D790/ISO 178 at a testing speed of 10 mm/min;
3. rockwell hardness: testing according to ASTM D785, with a test temperature of 23 ℃;
4. IZOD notched impact strength: the test was carried out according to ASTM D256/ISO179, at a test temperature of 23 ℃.
TABLE 3 Performance test results of bio-based straw composites
Figure BDA0003024838210000101
Figure BDA0003024838210000111
As can be seen from the detection data in tables 1 and 3 and examples 1 to 8, the bio-based straw composite material prepared in examples 1 to 8 by using the wheat straw fibers prepared in the wheat straw fiber preparation examples 1 to 3 of the present application has the tensile strength of 40.1 to 40.7MPa, the bending strength of 62 to 69MPa, excellent mechanical properties and good impact resistance, and compared with the R307Y polypropylene in table 1, the difference in mechanical properties is not obvious, which indicates that the mechanical properties of the bio-based straw composite material prepared in the present application reach the standard of conventional plastics.
In examples 9 to 11, on the basis of example 1, the nano toughening material prepared in the present application is added, and as can be seen from the data in table 3, the tensile strength of the bio-based straw composite material is increased to 43.5 to 44.1MPa, the bending strength is increased to 73 to 79MPa, and the mechanical property is significantly increased.
In contrast, in example 12, the skeleton material a was not used when the nano toughening material was prepared, and in example 13, the skeleton material B was not used when the nano toughening material was prepared, and it is shown from the data in table 3 that the mechanical properties of the composite materials prepared in examples 12 and 13 were reduced compared to those of examples 9 to 11.
In example 14, since PMMA is not used in the preparation of the nano toughening material, the compression strength and the bending strength of the composite material prepared in example 14 were 42.6MPa and 73MPa, and the mechanical properties were improved as compared with example 1, but the compression strength, the bending strength, the elongation at break, and other properties were all reduced as compared with examples 9 to 11, indicating that PMMA can increase the mechanical properties of the composite material.
In examples 15-17, on the basis of example 1, maleic anhydride grafted polylactic acid and KH550 silane coupling agent are used as compatilizers, and compared with example 1, the impact strength of the bio-based straw composite material prepared in examples 15-17 is not greatly changed, but the flexural strength and tensile strength are obviously improved.
In the example 18 and the example 19, the maleic anhydride grafted polylactic acid and the KH550 silane coupling agent are separately added, and the detection shows that the tensile strength, the bending strength and the bending modulus of the bio-based straw composite material are reduced, which indicates that the compatibility of the composite material can be enhanced and the mechanical property can be improved by the matching of the maleic anhydride grafted polylactic acid and the KH550 silane coupling agent.
Example 20 on the basis of example 1, the nano toughening material and the compatibilizer prepared in the present application are added, and compared with examples 9 to 11 and examples 15 to 17, the mechanical properties of the composite material prepared in example 20 are improved, and example 20 is the most preferred example.
In comparative example 1, the titanate coupling agent is not added in the spraying liquid when the wheat straw fiber is prepared, in comparative example 2, the maleic anhydride grafted polypropylene wax is not added in the spraying liquid when the wheat straw fiber is prepared, so that the tensile strength and the bending strength of the bio-based composite materials prepared in comparative example 1 and comparative example 2 are reduced, and the mechanical property is reduced.
In the comparative example 3, when the wheat straw fiber is prepared, microwave radiation is not used, so that the polarity of the surface of the wheat straw fiber is higher, the compatibility with polypropylene is reduced, and the mechanical property is weakened.
Comparative example 4 when preparing wheat straw fiber, without soaking xylitol enzyme solution, the degree of combination of wheat straw fiber and polypropylene is reduced, the interface performance is poor, and the mechanical properties are reduced.
In the comparative example 5, the wheat straw fiber is not treated, so that the prepared bio-based straw composite material has the tensile strength of only 14MPa, the bending strength of 26MPa and the impact strength of 3J/M, and has larger performance difference compared with the example 1, which shows that the wheat straw fiber prepared by the method has good compatibility with polypropylene and can effectively improve the mechanical property of the bio-based composite material.
Compared with the example 1, the mechanical properties of the composite materials prepared in the comparative examples 6 and 7 are reduced, which shows that the compatilizer and the nano toughening material have the effect of improving the mechanical properties of the composite material.
Comparative example 8 is bio-based straw composite plastic prepared by the prior art, the tensile strength of the bio-based straw composite plastic is 27MPa, the bending strength of the bio-based straw composite plastic is 33MPa, and the complete modulus of the bio-based straw composite plastic is 1280 MPa.
Application example
The bio-based straw composite material prepared by the application can be used for preparing ice cream sticks, furniture daily necessities, tableware and wood-like products, and the preparation of the ice cream sticks is taken as an example.
Application example 1: the bio-based straw composite material prepared in example 20 was heated to 140 ℃, added into a hot runner mold, and subjected to pressure maintaining at 1.8MPa for 1.5min, followed by natural cooling, to obtain ice cream sticks having a length of 5cm, a thickness of 0.3cm, and a width of 1.2 cm.
Application example 2: the bio-based straw composite material prepared in example 20 was heated to 160 ℃, added into a mold, and pressure-maintained at 2.0MPa for 1.0min, and naturally cooled to prepare ice cream sticks having a length of 5cm, a thickness of 0.3cm, and a width of 1.2 cm.
Application example 3: the melt prepared in example 20 was put into a mold, and pressure was maintained at 2.2MPa for 0.5min, followed by natural cooling, to obtain an ice cream bar having a length of 5cm, a thickness of 0.3cm and a width of 1.2 cm.
Application example 4: the difference from application example 1 is that when the ice cream stick is cooled to room temperature, the ice cream stick is put into a sodium hydroxide solution with the mass fraction of 5%, treated at 80 ℃ for 60min, washed to be neutral by deionized water, then put into a mildew-proof treatment liquid, kept at-0.08 MPa for 2h, and dried at 45 ℃ for 2h, wherein the mass ratio of the ice cream stick to the mildew-proof treatment liquid is 1:1.5, and the mildew-proof treatment liquid is prepared by mixing benzoic acid and water according to the mass ratio of 1: 0.1.
Application example 5: the difference from application example 1 is that when the ice cream stick is cooled to room temperature, the ice cream stick is put into a sodium hydroxide solution with the mass fraction of 7%, treated at 90 ℃ for 50min, washed to be neutral by deionized water, put into a mildew-proof treatment liquid, kept at-0.1 MPa for 1h, and dried at 45 ℃ for 2h, wherein the mass ratio of the ice cream stick to the mildew-proof treatment liquid is 1:1.8, and the mildew-proof treatment liquid is prepared by mixing benzoic acid and water according to the mass ratio of 1: 0.1.
Application examples 6 to 14: the difference from application example 4 is that the mildew-proof treatment liquid is prepared by mixing the raw materials in the table 4, the dill seed essential oil is selected from Jinyu biotechnology limited company in Jian City, the tea extract with the product number of JY085 is selected from Yinxinglu biotechnology limited company with the product number of XL180614, and the litsea cubeba essential oil is selected from Huatianbao Chinese herbal medicine biological product factory in Jian City, and the product number of HTB 178.
Application example 15: the difference from application example 6 is that the ice cream stick was not treated in sodium hydroxide solution.
TABLE 4 formulation of raw materials for the mildew-proof treatment solutions of application examples 6 to 14
Figure BDA0003024838210000131
Application example Performance detection
Ice cream sticks were prepared according to the method in application examples 1-15, and an accelerated mould corrosion test was performed according to the following method: (1) preparing a mould corrosion solution: according to the standard in ASTMG21, taking 5 strains (Aspergillus niger, Chaetomium globosum, Aureobasidium pullulans, Scopulariopsis virens and Penicillium pinophilum), inoculating the strains and a potato-glucose culture medium, culturing for 7-20 days at 28-30 ℃, and preparing 5 mould corrosive liquids with equal concentration by using nutrient salt solution; (2) preparing nutrient salt culture medium according to ASRMG21 standard, pouring culture medium solution into a sterile culture dish with a thickness of 3-6mm, and placing ice cream stick on the surface after the culture medium is solidified; (3) the 5 kinds of mould corrosive liquid are mixed uniformly in equal amount and then sprayed on the ice cream stick, and the ice cream stick is put in a constant temperature and humidity box for accelerated corrosion, wherein the temperature of a corrosion test is 28 ℃, the humidity is 85%, and the time is 28 days.
After the ice cream sticks are subjected to accelerated corrosion according to the method, the ice cream sticks are taken out to be detected according to the following method, the detection results are recorded in a table 5, 20 ice cream sticks in each group of application are taken for testing, and the average value of the test results is taken.
1. Tensile strength: detecting according to GB/T1040.6-2006, wherein the drawing speed is 2 mm/min;
2. bending strength: detecting according to GB/T9341-2008, wherein the loading speed is 2 mm/min;
3. impact strength: detecting according to GB/T1043.1-2008;
4. and (3) color testing: according to CIE1976L * a * b, detecting by a color system, testing for 6 times at different positions of each ice cream stick, taking an average value, and calculating the color change according to the following formula: delta E * ＝[(△L * ) 2 +(△a * ) 2 +(△b * ) 2 ] 1/2 In the formula: delta E * Is the color difference; +. DELTA L * The value is 0-100, which represents whitening, -. DELTA.L * Indicating blackening; a is * The value is-150- +150, + DELTAa * Indicates reddening, -. DELTA.a * Indicates a change of green, b * The value is-150- +150, and + delta b * Indicates yellowing, -. DELTA.b * Indicating a bluing.
TABLE 5 application examples 1-15 prepared ice cream stick mildew-proof and corrosion-proof test results
Figure BDA0003024838210000141
Figure BDA0003024838210000151
As can be seen from the data in Table 5, after the ice cream sticks prepared by the application examples 1-3 are subjected to accelerated corrosion by mold, the tensile strength, the full strength and the impact strength of the ice cream sticks are greatly different from those before accelerated corrosion is not carried out, and the color difference before and after corrosion is large, while after the ice cream sticks treated by the mildewproof treatment liquid in the application examples 4-5 are subjected to accelerated corrosion, the mechanical properties of the ice cream sticks are remarkably improved and the color difference is reduced compared with those of the application examples 1-3.
In application examples 6 to 8, after the ice cream sticks are treated by the mildew-proof treatment liquid prepared in the application example, the differences of the properties such as the tensile strength, the bending strength and the like of the ice cream sticks after accelerated corrosion are smaller than those of the ice cream sticks which are not subjected to corrosion in the application example 20, which shows that the mildew-proof treatment liquid has stronger mildew-proof and corrosion-proof effects.
In application examples 9 to 11, because the dill seed essential oil, the tea extract and the litsea cubeba essential oil are not added in the mildewproof treatment liquid respectively, the detection results show that the mechanical properties of the ice cream stick prepared in application examples 9 to 11 are remarkably reduced and the color difference is increased after accelerated corrosion is carried out on the ice cream stick compared with application examples 6 to 8, which shows that the dill seed essential oil, the tea extract and the litsea cubeba essential oil can improve the antiseptic and mildewproof effects of the ice cream stick
In application example 12, as the dill seed essential oil and the tea extract are not added to the mildewproof treatment liquid, it can be seen from the data in table 5 that the mildewproof effect of the ice cream stick in application example 12 is remarkably reduced compared with application examples 6 to 8 and application examples 9 to 10, which shows that the dill seed essential oil and the tea extract have a better synergistic mildewproof effect.
In application example 13, because the dill seed essential oil and the litsea cubeba essential oil are not added in the mildewproof treatment liquid, compared with application examples 6 to 9 and application example 11, the tensile strength, the bending strength and the shore hardness of the ice cream stick in application example 13 are remarkably reduced, which shows that the dill seed essential oil and the litsea cubeba essential oil have better synergistic effect.
In application example 14, because the tea extract and the litsea cubeba essential oil are not added in the mildewproof treatment liquid, the mechanical properties of the ice cream stick in application example 14 are greatly different before and after the accelerated corrosion test, and the color difference is obviously increased, which shows that the litsea cubeba essential oil and the tea extract have a good mildewproof synergistic effect.
In application example 15, the ice cream stick is not treated with the sodium hydroxide solution, and as can be seen from the data in table 5, compared with application example 6, the mildew-proof effect of the ice cream stick treated in application example 15 is reduced, and the color difference is large, which indicates that the mildew-proof effect of the ice cream stick can be enhanced by pretreating the ice cream stick with the sodium hydroxide solution.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (2)

1. The preparation method of the ice cream stick is characterized by comprising the following steps: adding the melt or the bio-based straw composite material into a mold, maintaining the pressure for 0.5-1.5min at 1.8-2.2MPa, naturally cooling to obtain an ice cream bar, and heating the bio-based straw composite material to 140-160 ℃ before adding the bio-based straw composite material into the mold;
when the ice cream stick is cooled to room temperature, the ice cream stick is placed into a sodium hydroxide solution with the mass fraction of 5-7%, treated at 80-90 ℃ for 50-60min, washed to be neutral by deionized water, placed into a mildew-proof treatment liquid, kept at the pressure of- (0.08-0.1) MPa for 1-2h, dried at 45-50 ℃ for 1-2h, and the mass ratio of the ice cream stick to the mildew-proof treatment liquid is 1: 1.5-1.8; the mildew-proof treatment liquid is prepared from the following components in parts by weight: 0.8-1.3 parts of dill seed essential oil, 0.4-0.8 part of tea extract, 1-1.5 parts of litsea cubeba essential oil and 2-3 parts of distilled water;
the melt or bio-based straw composite material comprises the following components in parts by weight: 35-55 parts of wheat straw fiber, 45-65 parts of polypropylene, 1-3 parts of compatilizer and 6-12 parts of nano tough material;
the preparation method of the melt or bio-based straw composite material comprises the following steps:
crushing polypropylene, sieving with a 120-mesh sieve, mixing with wheat straw fiber, drying at 80-85 ℃ for 2h, adding a compatilizer and a nano toughening material, extruding at 140-190 ℃ to obtain a molten mass, and bracing, cooling and granulating the molten mass to obtain the bio-based straw composite material;
the preparation method of the wheat straw fiber comprises the following steps: (1) crushing and drying wheat straws to form wheat straw fibers, mixing 1-2 parts by weight of titanate coupling agent, 0.4-0.8 part by weight of maleic anhydride grafted polypropylene wax and 5-10 parts by weight of absolute ethyl alcohol to form spraying liquid, uniformly spraying the spraying liquid on the wheat straw fibers, and carrying out microwave radiation for 3-5min under the power of 800-900W, wherein the mass ratio of the wheat straw fibers to the spraying liquid is 1: 0.5-0.8; (2) putting the wheat straw fiber treated in the step (1) into a xylitol enzyme solution with the concentration of 60-80%, soaking for 3-5h at 50-80 ℃, washing, and drying in vacuum, wherein the mass ratio of the wheat straw fiber to the xylitol enzyme solution is 1: 1.3-1.5;
each part by weight of the nano tough material comprises the following components in parts by weight: 4.5-6 parts of nano zinc oxide, 2-3 parts of EPDM (ethylene-propylene-diene monomer), 10-14 parts of PMMA (polymethyl methacrylate), 3.4-5.2 parts of carbon fiber, 1.6-2.8 parts of glass fiber, 0.3-0.6 part of dispersing agent, 0.4-0.8 part of adhesive and 5-10 parts of silica sol;
the preparation method of the nano toughening material comprises the following steps: (1) uniformly mixing carbon fibers and glass fibers, adding the mixture into silica sol, uniformly mixing under the pressure of- (0.5-1) MPa, drying and crushing to form a framework material A;
(2) adding nano zinc oxide into 40-50% adhesive solution prepared by mixing adhesive and water, uniformly mixing, uniformly spraying the mixture on EPDM, and vacuum drying to form a framework material B;
(3) mixing the framework material A, the framework material B, the dispersant and PMMA, heating to 130-140 ℃, uniformly mixing, drying for 4-6h at 60-80 ℃, and crushing to prepare a nano toughening material;
the compatilizer is maleic anhydride grafted polylactic acid and KH550 silane coupling agent with the mass ratio of 1: 0.6-0.9.
2. The preparation method of the ice cream bar according to claim 1, wherein the dispersant is one or a combination of several of nonylphenol polyoxyethylene ether, sulfonate copolymer and polyacrylamide.
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