CN115403851A - Thermoplastic composite material and preparation method thereof - Google Patents
Thermoplastic composite material and preparation method thereof Download PDFInfo
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- CN115403851A CN115403851A CN202211271110.2A CN202211271110A CN115403851A CN 115403851 A CN115403851 A CN 115403851A CN 202211271110 A CN202211271110 A CN 202211271110A CN 115403851 A CN115403851 A CN 115403851A
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
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Abstract
The invention discloses a thermoplastic composite material and a preparation method thereof, wherein the thermoplastic composite material comprises the following raw materials: thermoplastic material, flame-retardant filler, toughening agent, compatibilizer and antioxidant. The thermoplastic composite material disclosed by the invention not only has good mechanical properties such as tensile impact strength and the like, but also has good flame retardant property and aging resistance.
Description
Technical Field
The invention belongs to the technical field of plastics, and particularly relates to a thermoplastic composite material and a preparation method thereof.
Background
The thermoplastic material is a high polymer material which has plasticity at a certain temperature, is solidified after cooling and can repeat the process, and can be recycled and reprocessed for reuse. The thermoplastic material mainly comprises polyolefins, polyether polyesters, aromatic heterocyclic polymers and the like, and the molecular structure of the thermoplastic material does not have active groups and does not generate linear intermolecular crosslinking when heated. Thermoplastic composite materials are generally prepared by injection molding of pure plastics and are often unsatisfactory in mechanical properties. Chinese patent CN106751091A discloses a thermoplastic composite material and a preparation method thereof, comprising the following steps: mixing corn stalk fiber powder with an auxiliary agent, and then adding recycled polystyrene, recycled high-density polyethylene and a styrene-butadiene-styrene block polymer; extruding and granulating the mixture to obtain a thermoplastic composite material; the thermoplastic composite material prepared by the patent has good mechanical properties, and in addition, the corn straw fiber powder is added, so that the thermoplastic composite material has environmental protection, but the toughness and the aging resistance of the thermoplastic composite material need to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a thermoplastic composite material and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a flame-retardant filler, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of (95-115): (8-13): (10-16): (4-8): (2-5), carrying out premixing treatment for 30-40min under the process conditions of a heating temperature of 185-195 ℃, a loading pressure of 12-15MPa and a stirring speed of 85-110rpm, and then carrying out extrusion molding at a temperature of 185-195 ℃ under a pressure of 2-5MPa to obtain the thermoplastic composite material.
The thermoplastic composite material obtained by remelting and recasting recycled second-hand waste thermoplastic plastics has the problem of poor mechanical properties such as tensile strength, bending strength, impact strength and the like, so that the improvement needs to be carried out by optimizing a processing process and adding additives such as toughening and the like. The invention provides a preparation method of a thermoplastic composite material, which is used for improving mechanical properties such as toughness, tensile strength and the like of the thermoplastic composite material. The thermoplastic composite material has an isotropic microstructure, and macroscopically exhibits significantly improved indicators including tensile and impact strength, and also exhibits good ultraviolet aging resistance.
The thermoplastic material is at least one of polyethylene plastic, polypropylene plastic, polyvinyl chloride plastic, polycarbonate plastic, polystyrene plastic and polyamide plastic.
In a preferable scheme, the thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of (1-5) to (1-5).
Wherein, the molecular weight of the polyethylene plastic is as follows: 4.2-4.6 ten thousand; polypropylene plastic, molecular weight: 1.2-1.4 ten thousand; polyvinyl chloride plastic, molecular weight: 7-7.5 ten thousand; the above plastics are all recycled second-hand waste plastics.
The compatibilizer is at least one of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester.
In a preferred scheme, the compatibilizer is a mixture of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester in a mass ratio of (1-5) to (1-4) to (1-2.5).
The antioxidant is at least one of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol).
In a preferable scheme, the antioxidant is a mixture of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of (0.5-3) to (0.1-1.5) to (1-4.2).
The preparation method of the flame-retardant filler comprises the following steps:
mixing the regenerated carbon fiber with 30-70wt% of acetone aqueous solution according to the mass ratio of 1 (5-10), and carrying out ultrasonic treatment for 0.5-1h under the conditions that the frequency is 20-30kHz and the power is 200-350W; then adding nitric acid with the concentration of 7-10mol/L and the mass of 100-200% of the regenerated carbon fiber, and continuing ultrasonic treatment for 1-2h at 75-85 ℃; filtering, washing with water to neutrality, and oven drying at 70-80 deg.C for 3-5 hr; calcining at 500-600 deg.C for 3-5h to obtain pretreated carbon fiber; mixing isopropyl distearoyloxy aluminate, gamma-glycidyl ether oxypropyltrimethoxysilane, pretreated carbon fiber and isopropanol in a mass ratio of (1-2) to (10-20) to (60-80), stirring at 50-70 ℃ and 200-500rpm for 1-3h, filtering, washing with isopropanol, and drying at 70-90 ℃ for 1-3h to obtain the flame-retardant filler.
Wherein, the regenerated carbon fiber is the carbon fiber obtained by recovering the waste carbon fiber reinforced composite material (CFRP) after mechanical rolling and chemical treatment, and the fiber length of the regenerated carbon fiber is 0.5-50mm.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1 (3.5-6.2), and performing ultrahigh pressure treatment at 530-540MPa for 23-28min to obtain starch paste;
a2, adding 1.5-2mol/L hydrochloric acid with the mass of 5-6.3% of the starch paste, and then carrying out microwave treatment for 18-22min at the frequency of 475-480MHz and the power of 480-500W to obtain acidified starch paste;
a3, stirring at the rotating speed of 20-25rpm for 25-35min under the water bath heating state at the temperature of 60-62 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1 (6.5-8);
a4, adding 12-15% of lecithin and 5-7% of oleamide into the zein solution respectively, and carrying out ultrasonic treatment at 57-60 ℃ with the frequency of 41-43kHz and the power of 330-350W for 30-40min to obtain modified zein;
a5, mixing the acidified starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole according to the mass ratio of (16.5-19), (13.5-16.2), (8.6-11.5), (2.3-5.6) and (45-49), putting into a reaction kettle, and reacting for 70-90min according to the process parameters of the temperature of 126-130 ℃, the pressure of 16-18.5MPa and the stirring speed of 10-30rpm to obtain an intermediate product C;
a6 is cooled to 65-70 ℃, 3-methylbenzoic acid barium salt accounting for 3-5% of the mass of the intermediate product C is added into the intermediate product C, ultrasonic treatment is carried out for 30-40min at the frequency of 39-40kHz and the power of 320-330W, then the temperature is cooled to 4-7 ℃, standing is carried out for 160-200min at the temperature, then centrifugation is carried out for 3-6min at the rotating speed of 7000-8000rpm, and sediment B is taken;
and A7, drying the precipitate B under reduced pressure by using the technological parameters of 68-70 ℃ of temperature, 3-6kPa of pressure, 10-30rpm of stirring speed and 130-170min of drying time to obtain the toughening agent.
The corn starch has wide source and low price, and has various good special properties after being modified. The ultrahigh pressure treatment can enable the crystal configuration of the corn starch to be damaged and recombined, so that the rheological property and the gelatinization kinetics of the corn starch are changed, after a part of hydrogen bonds in the corn starch are damaged, active branched chains with high free energy are formed in an acid environment, so that the acidified starch paste can be fully grafted and crosslinked with modified zein, polyethyleneimine and isocyanate in a subsequent anisole environment, and the toughening agent with high toughness and strong adhesion is obtained. And the molecular structure of the obtained acidified starch paste becomes more isotropic after ultrahigh pressure and acidification treatment, so that thermoplastic raw materials can be rearranged by optimizing the dynamic trend of the thermoplastic raw materials under the guidance of active branched chains of acidified starch molecules, and as a result, the thermoplastic composite material obtains an isotropic microstructure, so that the highly uniform and approximate microstructure brings higher impact resistance, tensile resistance, compression resistance and shear resistance macroscopic properties.
Zein with alpha-spirochetes and beta-sheets having amino-terminal-NH 2 And carboxyl-COOH, and also has a rod-shaped molecular configuration and abundant side chains, and the molecular characteristics of the carboxyl-COOH make the carboxyl-COOH have good binding capacity and oxygen resistance, abrasion resistance and grease resistance. According to the invention, zein is dissolved in dimethyl sulfoxide, so that peptide chain crosslinking is carried out on the zein under the action of lecithin and oleamide, and a spatial three-dimensional molecular structure with stronger elasticity is obtained, which is due to strong nonpolar affinity among the lecithin, the oleamide and the zein. Furthermore, oleamide also has scratch resistance, stain resistance, abrasion resistance, and can enhance the durability of the resulting thermoplastic composite.
The polyacetimide has strong adhesion and can enhance the connection strength among various thermoplastic raw materials. The modified zein has good compatibility with the nitrogen-containing polyimide containing nitrogen atoms due to the incorporation of the nitrogen-containing group of the oleamide.
The invention utilizes the barium salt of 3-methylbenzoate to precipitate and separate out flocculent intermediate products to obtain the toughening agent, wherein the barium element contained in the toughening agent can be synergized with 4,4 '-thiobis (6-tert-butyl-2-methylphenol) in the adopted compound antioxidant, and the electron cloud energy state distribution between the barium element and the 4,4' -thiobis (6-tert-butyl-2-methylphenol) is beneficial to timely 'extinguishing' free radicals with oxidation destruction capability generated by ultraviolet excitation of the whole material.
The isocyanate is at least one of diphenylmethane diisocyanate and benzoyl isothiocyanate.
The molecular structure of isocyanate contains unsaturated bonds, so that the isocyanate has high reaction activity and is easy to react with organic matters with active groups to generate polyurethane elastomers, and the elastomers can make a considerable contribution to the overall elasticity of the material. A part of hydroxyl contained in the acidified starch paste can react with isocyanate to generate aminomethyl acid ester; the amino group in the modified zein can generate urea with isocyanate, and the urea can provide certain oxidation resistance and corrosion resistance for the whole material.
In a preferred embodiment, the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in a mass ratio of (1-3) to (1-3).
The benzene structure in the diphenylmethane diisocyanate has non-polarity, so that the compatibility between the obtained toughening agent and the adopted thermoplastic raw material is improved, the integral connection strength of the material is enhanced, and the mechanical strength including the tensile impact strength is improved in a macroscopic view; in addition to the improvement of compatibility contributed by the nonpolar group, the benzoyl isothiocyanate can generate hydrogen bonds between sulfur elements on specific sites contained in the benzoyl isothiocyanate and sulfur bonds in the modified zein, so that the bonding strength between raw materials in the toughening agent is enhanced, the mismatching degree of each phase in the whole material is also reduced, the microstructure of the material shows higher isotropy, the mechanical strength including the tensile impact strength of the material is obviously improved in a macroscopic view, and the material has good toughness and strength.
In a more preferred embodiment, the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in a mass ratio of 2.
According to the invention, the diphenylmethane diisocyanate and the benzoyl isothiocyanate are combined, so that the strength and the oxidation resistance of the obtained thermoplastic composite material are improved, the strength and the oxidation resistance are supposed to be related to the cooperative reduction of the mismatching degree caused by the molecular weight difference of the two isocyanates, and the combination of the two reduces the integral free energy of the material, so that the material shows more stable properties.
The invention has the beneficial effects that: the thermoplastic composite material is obtained by extrusion molding after the thermoplastic material, the flame-retardant filler, the toughening agent, the compatibilizer and the antioxidant are heated, pressurized and premixed, and not only has good mechanical properties such as tensile impact strength and the like, but also has good flame retardant property and aging resistance. The toughening agent added in the raw material formula is prepared by taking acidified starch paste, modified zein, polyethyleneimine, isocyanate and anisole as raw materials, and can obviously improve the isotropy of the microstructure of the thermoplastic composite material and obtain macroscopic mechanical strength improvement.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some of the raw materials in this application:
corn starch, CAS:9005-25-8, chemical Limited for Jinan Fuhong chemical Limited, cat #: XFV0809.
Zein, CAS:9010-66-6, sienprevis bioengineering, ltd, cat no: 232.
lecithin, CAS:8002-43-5, hubei Runsheng Biotechnology Ltd, cat # O: l20-03.
Polyethyleneimine, CAS:9002-98-6, molecular weight: 1 ten thousand, shandong Li ang New Material science and technology Co., ltd, type: LA-7Q.
Diphenylmethane diisocyanate, CAS:5101-68-8.
Benzoyl isothiocyanate, CAS:532-55-8.
Polytetrahydrofuran, CAS:24979-97-3, molecular weight: 1000 Hubei Jiulong chemical Co., ltd., cat #: 00084.
coconut oil fatty acid diacetylamide, CAS:61791-31-9.
Dimethyl 1, 4-cyclohexanedicarboxylate, CAS:94-60-0.
2, 4-di-tert-butylphenol, CAS:96-76-4.
Tert-butyl p-hydroxyanisole, CAS:25013-16-5.
4,4' -thiobis (6-tert-butyl-2-methylphenol), CAS:96-66-2.
Barium 3-methylbenzoate, CAS:68092-47-7.
Copolymer of styrene and maleic anhydride, CAS:9011-13-6, molecular weight: 2 million, my shanghai mairei chemical technologies, inc.
Example 1
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions that the heating temperature is 190 ℃, the loading pressure is 14MPa and the stirring speed is 100rpm, and then extruding and molding at 190 ℃ under the pressure of 2.5MPa to obtain the thermoplastic composite material with the length-diameter ratio of 10 strips.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester according to the mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The toughening agent is a copolymer of styrene and maleic anhydride.
Example 2
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions that the heating temperature is 190 ℃, the loading pressure is 14MPa and the stirring speed is 100rpm, and then extruding and molding at 190 ℃ under the pressure of 2.5MPa to obtain the thermoplastic composite material with the length-diameter ratio of 10 strips.
The thermoplastic material is a mixture consisting of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic according to a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester according to the mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ so as to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1;
a2, adding 15% of lecithin and 7% of oleamide into the zein solution respectively, and carrying out ultrasonic treatment at 60 ℃ with the frequency of 43kHz and the power of 350W for 40min to obtain modified zein;
a3, mixing the modified zein, the polyethyleneimine, the isocyanate and the anisole in a mass ratio of 15; the isocyanate is benzoyl isothiocyanate;
a4 is cooled to 70 ℃, barium 3-methylbenzoate accounting for 4% of the mass of the intermediate product C is added into the intermediate product C, ultrasonic treatment is carried out for 30min at the frequency of 40kHz and the power of 320W, then the temperature is cooled to 5 ℃, standing is carried out for 180min at the temperature, and then centrifugation is carried out for 5min at the rotation speed of 8000rpm, and a precipitate B is taken;
and A5, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 3
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions of a heating temperature of 190 ℃, a loading pressure of 14MPa and a stirring speed of 100rpm, and then extruding and molding at 190 ℃ under a pressure of 2.5MPa to obtain the thermoplastic composite material with a length-diameter ratio of 10 strips.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester in a mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1;
a2, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1;
a3, adding lecithin accounting for 15% of the mass of the zein solution and oleamide accounting for 7% of the mass of the zein solution respectively, and carrying out ultrasonic treatment for 40min at 60 ℃ at the frequency of 43kHz and the power of 350W to obtain modified zein;
a4, mixing the starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole in a mass ratio of 18; the isocyanate is benzoyl isothiocyanate;
a5, cooling to 70 ℃, adding barium 3-methylbenzoate with the mass of 4% of that of the intermediate product C into the intermediate product C, performing ultrasonic treatment for 30min at the frequency of 40kHz and the power of 320W, cooling to 5 ℃, standing for 180min at the temperature, centrifuging for 5min at the rotation speed of 8000rpm, and taking a precipitate B;
and A6, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 4
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions of a heating temperature of 190 ℃, a loading pressure of 14MPa and a stirring speed of 100rpm, and then extruding and molding at 190 ℃ under a pressure of 2.5MPa to obtain the thermoplastic composite material with a length-diameter ratio of 10 strips.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester in a mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1;
a2, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1;
a3, adding 15% of lecithin and 7% of oleamide by mass into the zein solution respectively, and carrying out ultrasonic treatment at 60 ℃ for 40min at the frequency of 43kHz and the power of 350W to obtain modified zein;
a4, mixing the starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole in a mass ratio of 18; the isocyanate is benzoyl isothiocyanate;
a5, cooling to 70 ℃, adding barium 3-methylbenzoate with the mass of 4% of that of the intermediate product C into the intermediate product C, performing ultrasonic treatment for 30min at the frequency of 40kHz and the power of 320W, cooling to 5 ℃, standing for 180min at the temperature, centrifuging for 5min at the rotation speed of 8000rpm, and taking a precipitate B;
and A6, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 5
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions that the heating temperature is 190 ℃, the loading pressure is 14MPa and the stirring speed is 100rpm, and then extruding and molding at 190 ℃ under the pressure of 2.5MPa to obtain the thermoplastic composite material with the length-diameter ratio of 10 strips.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester according to the mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1;
a2, adding 2mol/L hydrochloric acid with the concentration of 2mol/L and the mass of 6% of the starch paste, and then carrying out microwave treatment for 20min at the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, mixing the acidified starch paste, polyethyleneimine, isocyanate and anisole according to a mass ratio of 18; the isocyanate is benzoyl isothiocyanate;
a4 is cooled to 70 ℃, barium 3-methylbenzoate accounting for 4% of the mass of the intermediate product C is added into the intermediate product C, ultrasonic treatment is carried out for 30min at the frequency of 40kHz and the power of 320W, then the temperature is cooled to 5 ℃, standing is carried out for 180min at the temperature, and then centrifugation is carried out for 5min at the rotation speed of 8000rpm, and a precipitate B is taken;
and A5, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 6
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions that the heating temperature is 190 ℃, the loading pressure is 14MPa and the stirring speed is 100rpm, and then extruding and molding at 190 ℃ under the pressure of 2.5MPa to obtain the thermoplastic composite material with the length-diameter ratio of 10 strips.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester according to the mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water in a mass ratio of 1;
a2, adding 2mol/L hydrochloric acid with the concentration of 2mol/L and the mass of 6% of the starch paste, and then carrying out microwave treatment for 20min at the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ so that zein is dissolved in dimethyl sulfoxide; the mass ratio of the zein to the dimethyl sulfoxide is 1; then carrying out ultrasonic treatment at 60 ℃ with the frequency of 43kHz and the power of 350W for 40min to obtain a zein solution;
a4, mixing the acidified starch paste, the zein solution, the polyethyleneimine, the isocyanate and the anisole in a mass ratio of 18; the isocyanate is benzoyl isothiocyanate;
a5, cooling to 70 ℃, adding barium 3-methylbenzoate with the mass of 4% of that of the intermediate product C into the intermediate product C, performing ultrasonic treatment for 30min at the frequency of 40kHz and the power of 320W, cooling to 5 ℃, standing for 180min at the temperature, centrifuging for 5min at the rotation speed of 8000rpm, and taking a precipitate B;
and A6, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 7
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions of a heating temperature of 190 ℃, a loading pressure of 14MPa and a stirring speed of 100rpm, and then extruding and molding at 190 ℃ under a pressure of 2.5MPa to obtain the thermoplastic composite material with a length-diameter ratio of 10 strips.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester according to the mass ratio of 3.
The antioxidant is a mixture of 2, 4-di-tert-butylphenol and tert-butyl p-hydroxyanisole in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass of 6% of the starch paste, and then carrying out microwave treatment for 20min at the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1;
a4, adding lecithin accounting for 15% of the mass of the zein solution and oleamide accounting for 7% of the mass of the zein solution respectively, and carrying out ultrasonic treatment for 40min at 60 ℃ at the frequency of 43kHz and the power of 350W to obtain modified zein;
a5, mixing the acidified starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole in a mass ratio of 18; the isocyanate is benzoyl isothiocyanate;
a6, cooling to 70 ℃, adding barium 3-methylbenzoate with the mass being 4% of that of the intermediate product C into the intermediate product C, carrying out ultrasonic treatment for 30min at the frequency of 40kHz and the power of 320W, cooling to 5 ℃, standing for 180min at the temperature, centrifuging for 5min at the rotation speed of 8000rpm, and taking a precipitate B;
and A7, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 8
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions that the heating temperature is 190 ℃, the loading pressure is 14MPa and the stirring speed is 100rpm, and then extruding and molding at 190 ℃ under the pressure of 2.5MPa to obtain the thermoplastic composite material with the length-diameter ratio of 10 strips.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester according to the mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass of 6% of the starch paste, and then carrying out microwave treatment for 20min at the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1;
a4, adding 15% of lecithin and 7% of oleamide by mass into the zein solution respectively, and carrying out ultrasonic treatment at 60 ℃ for 40min at the frequency of 43kHz and the power of 350W to obtain modified zein;
a5, mixing the acidified starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole in a mass ratio of 18; the isocyanate is diphenylmethane diisocyanate;
a6, cooling to 70 ℃, adding barium 3-methylbenzoate with the mass of 4% of that of the intermediate product C into the intermediate product C, performing ultrasonic treatment for 30min at the frequency of 40kHz and the power of 320W, cooling to 5 ℃, standing for 180min at the temperature, centrifuging for 5min at the rotation speed of 8000rpm, and taking a precipitate B;
and A7, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 9
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions that the heating temperature is 190 ℃, the loading pressure is 14MPa and the stirring speed is 100rpm, and then extruding and molding at 190 ℃ under the pressure of 2.5MPa to obtain the thermoplastic composite material with the length-diameter ratio of 10 strips.
The thermoplastic material is a mixture consisting of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic according to a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester according to the mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1;
a2, adding 2mol/L hydrochloric acid with the concentration of 2mol/L and the mass of 6% of the starch paste, and then carrying out microwave treatment for 20min at the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1;
a4, adding 15% of lecithin and 7% of oleamide by mass into the zein solution respectively, and carrying out ultrasonic treatment at 60 ℃ for 40min at the frequency of 43kHz and the power of 350W to obtain modified zein;
a5, mixing the acidified starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole in a mass ratio of 18; the isocyanate is benzoyl isothiocyanate;
a6, cooling to 70 ℃, adding barium 3-methylbenzoate with the mass of 4% of that of the intermediate product C into the intermediate product C, performing ultrasonic treatment for 30min at the frequency of 40kHz and the power of 320W, cooling to 5 ℃, standing for 180min at the temperature, centrifuging for 5min at the rotation speed of 8000rpm, and taking a precipitate B;
and A7, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 10
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 4, pre-mixing for 35min under the process conditions of a heating temperature of 190 ℃, a loading pressure of 14MPa and a stirring speed of 100rpm, and then extruding and molding at 190 ℃ under a pressure of 2.5MPa to obtain the thermoplastic composite material with a length-diameter ratio of 10 strips.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester according to the mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water in a mass ratio of 1;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass of 6% of the starch paste, and then carrying out microwave treatment for 20min at the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1;
a4, adding lecithin accounting for 15% of the mass of the zein solution and oleamide accounting for 7% of the mass of the zein solution respectively, and carrying out ultrasonic treatment for 40min at 60 ℃ at the frequency of 43kHz and the power of 350W to obtain modified zein;
a5, mixing the acidified starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole in a mass ratio of 18; the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in a mass ratio of 2;
a6, cooling to 70 ℃, adding barium 3-methylbenzoate with the mass of 4% of that of the intermediate product C into the intermediate product C, performing ultrasonic treatment for 30min at the frequency of 40kHz and the power of 320W, cooling to 5 ℃, standing for 180min at the temperature, centrifuging for 5min at the rotation speed of 8000rpm, and taking a precipitate B;
and A7, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 11
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a flame-retardant filler, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 14, pre-mixing for 35min under the process conditions of a heating temperature of 190 ℃, a loading pressure of 14MPa and a stirring speed of 100rpm, and then extruding and molding at 190 ℃ under a pressure of 2.5MPa to obtain the thermoplastic composite material with an aspect ratio of 10 strips.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester in a mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water in a mass ratio of 1;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass of 6% of the starch paste, and then carrying out microwave treatment for 20min at the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1;
a4, adding lecithin accounting for 15% of the mass of the zein solution and oleamide accounting for 7% of the mass of the zein solution respectively, and carrying out ultrasonic treatment for 40min at 60 ℃ at the frequency of 43kHz and the power of 350W to obtain modified zein;
a5, mixing the acidified starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole in a mass ratio of 18; the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in a mass ratio of 2;
a6, cooling to 70 ℃, adding barium 3-methylbenzoate with the mass being 4% of that of the intermediate product C into the intermediate product C, carrying out ultrasonic treatment for 30min at the frequency of 40kHz and the power of 320W, cooling to 5 ℃, standing for 180min at the temperature, centrifuging for 5min at the rotation speed of 8000rpm, and taking a precipitate B;
and A7, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
The preparation method of the flame-retardant filler comprises the following steps: mixing gamma-glycidoxypropyltrimethoxysilane, regenerated carbon fiber and isopropanol in a mass ratio of 2.5 to 65, stirring at 65 ℃ and 300rpm for 1.5h, filtering, washing with isopropanol for 3 times, and drying at 85 ℃ for 2h to obtain the flame-retardant filler. The flame retardant properties of the thermoplastic composite obtained in example 11 were determined according to GB/T2406.2-2009, which has an oxygen index of 28.7%.
Example 12
A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a flame-retardant filler, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of 102 to 14.
The thermoplastic material is a mixture of polyethylene plastic, polypropylene plastic and polyvinyl chloride plastic in a mass ratio of 2.
The compatibilizer is a mixture consisting of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester according to the mass ratio of 3.
The antioxidant is a mixture consisting of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol) in a mass ratio of 2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass of 6% of the starch paste, and then carrying out microwave treatment for 20min at the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring for 30min at the rotating speed of 25rpm under the water bath heating state at the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1;
a4, adding 15% of lecithin and 7% of oleamide by mass into the zein solution respectively, and carrying out ultrasonic treatment at 60 ℃ for 40min at the frequency of 43kHz and the power of 350W to obtain modified zein;
a5, mixing the acidified starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole according to a mass ratio of 18; the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in a mass ratio of 2;
a6, cooling to 70 ℃, adding barium 3-methylbenzoate with the mass being 4% of that of the intermediate product C into the intermediate product C, carrying out ultrasonic treatment for 30min at the frequency of 40kHz and the power of 320W, cooling to 5 ℃, standing for 180min at the temperature, centrifuging for 5min at the rotation speed of 8000rpm, and taking a precipitate B;
and A7, drying the precipitate B under reduced pressure by using the technological parameters of 70 ℃ of temperature, 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
The preparation method of the flame-retardant filler comprises the following steps:
mixing the regenerated carbon fiber with a 60wt% acetone aqueous solution according to a mass ratio of 1; adding nitric acid with the concentration of 8.5mol/L and the mass of 150% of the regenerated carbon fiber, and continuing ultrasonic treatment for 1.5h at 78 ℃; filtering, washing with water to neutrality, and oven drying at 80 deg.C for 3 hr; calcining at 600 ℃ for 3.5 hours to obtain pretreated carbon fibers; mixing isopropyl distearoyloxy aluminate, gamma-glycidoxypropyltrimethoxysilane, pretreated carbon fiber and isopropanol in a mass ratio of 1.5. The flame retardant performance of the thermoplastic composite obtained in example 12 was determined with reference to GB/T2406.2-2009, which showed an oxygen index of 34.2%.
Test example 1
And (3) tensile impact test: the tensile impact strength of the thermoplastic composites obtained from the examples of the present invention was determined according to GB/T13525-1992, test method for tensile impact Properties of plastics. The test adopts a B type sample; the thickness of the sample is 1mm; in each case, 10 different samples were selected for the test, and the test results were averaged.
TABLE 1 tensile impact Strength of thermoplastic composites
Test example 2
Ultraviolet aging resistance test: first, according to GB/T16422.3-2014 Plastic laboratory light Source Exposure test method section 3: method A in fluorescent UV lamps ", the thermoplastic composite obtained from example 1 and examples 7 to 10 according to the invention was irradiated with aging. The temperature of the test environment was 23 ℃ and the relative humidity was 40%, and the ultraviolet aging irradiation treatment was carried out using a type 1A (UVA-340) fluorescent ultraviolet lamp. Then, the yellowing index Δ YI of the sample subjected to the ultraviolet aging irradiation treatment was measured according to HG/T3862-2006 "Plastic yellowing index test method". Each example tested 10 different samples for uv aging data and the test results were averaged.
TABLE 2 ultraviolet aging resistance of thermoplastic composites
The traditional thermoplastic plastics often have the problem of poor toughness, which is particularly shown in that the mechanical indexes of the traditional thermoplastic plastics, such as tensile strength, bending strength, shearing strength and the like, are low. In the field of recycled plastics, various second-hand thermoplastics are often remelted and recast simply, and the obtained simple polymer often has poor mechanical strength, poor tensile, compressive and bending resistance and even can not reach the standard of normal use. With the arousal of energy consumption and environmental awareness, a thermoplastic material production process capable of improving the toughness strength of a thermoplastic material and having a remarkable strength improvement effect on second-hand recycled plastic is increasingly required in the market. Therefore, the invention aims to provide a preparation method of a thermoplastic composite material, which not only can improve the toughness strength of the thermoplastic material, but also has a remarkable strength improvement effect on the second-hand recycled plastic. The method has simple process, safety, environmental protection, high efficiency, low cost and low cost, and the obtained thermoplastic composite material has an isotropic microstructure and macroscopically shows toughness strength including tensile impact strength and the likeThe index was remarkably improved, and also good ultraviolet ray aging resistance was exhibited. The corn starch has wide sources and low price, and often has various good special properties after various modification treatments. The ultrahigh pressure treatment can enable the crystal configuration of the corn starch to be damaged and recombined, so that the rheological property and the gelatinization kinetics of the corn starch are changed, after a part of hydrogen bonds in the corn starch are damaged, active branched chains with high free energy are formed in an acid environment, so that the acidified starch paste can be fully grafted and crosslinked with modified zein, polyethyleneimine and isocyanate in a subsequent anisole environment, and the toughening agent with high toughness and strong adhesion is obtained. And the molecular structure of the obtained acidified starch paste becomes more isotropic after ultrahigh pressure and acidification treatment, so that the thermoplastic raw materials can be rearranged by optimizing the dynamic trend of the thermoplastic raw materials under the guide of active branched chains of acidified starch molecules, and the result is that the thermoplastic composite material obtains an isotropic microstructure, so that the highly uniform and approximate microstructure brings the macroscopic properties of higher impact resistance, tensile resistance, compression resistance and shear resistance. Zein has alpha-spirochete and beta-sheet with amino terminal-NH 2 And carboxyl-COOH, and also has a rod-shaped molecular configuration and abundant side chains, and the molecular characteristics of the carboxyl-COOH make the carboxyl-COOH have good binding capacity and oxygen resistance, abrasion resistance and grease resistance. In the invention, zein is dissolved in dimethyl sulfoxide, so that peptide chain crosslinking is carried out on zein under the action of lecithin and oleic acid amide, a space three-dimensional molecular structure with stronger elasticity is obtained, and the zein has strong nonpolar affinity among the lecithin, the oleic acid amide and the zein. Furthermore, oleamide also has scratch resistance, stain resistance, abrasion resistance, and can enhance the durability of the resulting thermoplastic composite. The polyacetimide has strong adhesion and can enhance the connection strength among various thermoplastic raw materials. The modified zein has good compatibility with the nitrogen-containing polyimide containing nitrogen atoms due to the incorporation of the nitrogen-containing group of the oleamide. The molecular structure of isocyanate contains unsaturated bonds, so that the isocyanate has higher reactivity and is easy to react with some isocyanateThe organic matter with active group reacts to produce polyurethane elastomer, and the elastomer can make partial contribution to the elasticity of the whole material. A part of hydroxyl contained in the acidified starch paste can be reacted with isocyanate to generate aminomethyl acid ester; the amino group in the modified zein can generate urea with isocyanate, and the urea can provide certain oxidation resistance and corrosion resistance for the whole material. The benzene structure in the diphenylmethane diisocyanate has non-polarity, so that the compatibility between the obtained toughening agent and the adopted thermoplastic raw material is improved, the integral connection strength of the reinforced material is improved, and the mechanical strength including the tensile impact strength is improved in a macroscopic view; in addition to the improvement of compatibility contributed by the nonpolar group, the benzoyl isothiocyanate can generate hydrogen bonds between sulfur elements on specific sites contained in the benzoyl isothiocyanate and sulfur bonds in the modified zein, so that the bonding strength between raw materials in the toughening agent is enhanced, the mismatching degree of each phase in the whole material is also reduced, the microstructure of the material shows higher isotropy, the mechanical strength including the tensile impact strength of the material is obviously improved in a macroscopic view, and the material has good toughness and strength. According to the invention, the diphenylmethane diisocyanate and the benzoyl isothiocyanate are combined, so that the strength and the oxidation resistance of the obtained thermoplastic composite material are improved, the strength and the oxidation resistance are supposed to be related to the cooperative reduction of the mismatching degree caused by the molecular weight difference of the two isocyanates, and the combination of the two isocyanates reduces the integral free energy of the material, so that the material shows more stable properties. The barium-3-methylbenzoate is utilized to precipitate the flocculent intermediate product to obtain the toughening agent, the barium element contained in the toughening agent can be synergized with 4,4 '-thiobis (6-tert-butyl-2-methylphenol) in the adopted compound antioxidant, and the electron cloud energy state distribution between the barium element and the 4,4' -thiobis (6-tert-butyl-2-methylphenol) is beneficial to timely 'extinguishing' free radicals with oxidative destruction capability generated by ultraviolet excitation of the whole material.
Claims (8)
1. A method for preparing a thermoplastic composite material, comprising the steps of:
mixing a thermoplastic material, a flame-retardant filler, a toughening agent, a compatibilizer and an antioxidant according to a mass ratio of (95-115): (8-13): (10-16): (4-8): (2-5), carrying out premixing treatment for 30-40min under the process conditions of a heating temperature of 185-195 ℃, a loading pressure of 12-15MPa and a stirring speed of 85-110rpm, and then carrying out extrusion molding at a temperature of 185-195 ℃ under a pressure of 2-5MPa to obtain the thermoplastic composite material.
2. The method of preparing the thermoplastic composite of claim 1, wherein the flame retardant filler is prepared by:
mixing the regenerated carbon fiber with 30-70wt% of acetone aqueous solution according to the mass ratio of 1 (5-10), and carrying out ultrasonic treatment for 0.5-1h under the conditions that the frequency is 20-30kHz and the power is 200-350W; then adding nitric acid with the concentration of 7-10mol/L and the mass of 100-200% of the regenerated carbon fiber, and continuing ultrasonic treatment for 1-2h at 75-85 ℃; filtering, washing with water to neutrality, and oven drying at 70-80 deg.C for 3-5 hr; calcining at 500-600 deg.C for 3-5h to obtain pretreated carbon fiber; mixing isopropyl distearoyloxy aluminate, gamma-glycidyl ether oxypropyltrimethoxysilane, pretreated carbon fiber and isopropanol in a mass ratio of (1-2) to (10-20) to (60-80), stirring at 50-70 ℃ and 200-500rpm for 1-3h, filtering, washing with isopropanol, and drying at 70-90 ℃ for 1-3h to obtain the flame-retardant filler.
3. A method of making a thermoplastic composite according to claim 1, wherein: the thermoplastic material is at least one of polyethylene plastic, polypropylene plastic, polyvinyl chloride plastic, polycarbonate plastic, polystyrene plastic and polyamide plastic.
4. A method of making a thermoplastic composite according to claim 1, wherein: the compatibilizer is at least one of polytetrahydrofuran, coconut oil fatty acid diethylamide and 1, 4-cyclohexane dicarboxylic acid dimethyl ester.
5. A method of making a thermoplastic composite according to claim 1, wherein: the antioxidant is at least one of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxyanisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol).
6. The method of preparing the thermoplastic composite of claim 1, wherein the toughening agent is prepared by:
a1, mixing corn starch and water according to a mass ratio of 1 (3.5-6.2), and performing ultrahigh pressure treatment at 530-540MPa for 23-28min to obtain starch paste;
a2, adding 1.5-2mol/L hydrochloric acid with the mass of 5-6.3% of the starch paste, and then carrying out microwave treatment for 18-22min at the frequency of 475-480MHz and the power of 480-500W to obtain acidified starch paste;
a3, stirring at the rotating speed of 20-25rpm for 25-35min under the water bath heating state at the temperature of 60-62 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of the zein to the dimethyl sulfoxide is 1 (6.5-8);
a4, adding 12-15% of lecithin and 5-7% of oleamide into the zein solution respectively, and carrying out ultrasonic treatment at 57-60 ℃ with the frequency of 41-43kHz and the power of 330-350W for 30-40min to obtain modified zein;
a5, mixing the acidified starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole according to the mass ratio of (16.5-19), (13.5-16.2), (8.6-11.5), (2.3-5.6) and (45-49), putting into a reaction kettle, and reacting for 70-90min according to the process parameters of the temperature of 126-130 ℃, the pressure of 16-18.5MPa and the stirring speed of 10-30rpm to obtain an intermediate product C;
a6 is cooled to 65-70 ℃, 3-methylbenzoic acid barium salt accounting for 3-5% of the mass of the intermediate product C is added into the intermediate product C, ultrasonic treatment is carried out for 30-40min at the frequency of 39-40kHz and the power of 320-330W, then the temperature is cooled to 4-7 ℃, standing is carried out for 160-200min at the temperature, then centrifugation is carried out for 3-6min at the rotating speed of 7000-8000rpm, and sediment B is taken;
and A7, drying the precipitate B under reduced pressure by using the technological parameters of 68-70 ℃ of temperature, 3-6kPa of pressure, 10-30rpm of stirring speed and 130-170min of drying time to obtain the toughening agent.
7. The method of preparing a thermoplastic composite according to claim 6, wherein: the isocyanate is at least one of diphenylmethane diisocyanate and benzoyl isothiocyanate.
8. A thermoplastic composite characterized by: obtained by the production method according to any one of claims 1 to 7.
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