CN115403851B - Thermoplastic composite material and preparation method thereof - Google Patents
Thermoplastic composite material and preparation method thereof Download PDFInfo
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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 has good mechanical properties such as tensile impact strength and the like, and also has good flame retardant property and ageing 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
Thermoplastic materials are polymeric materials which have plasticity at a certain temperature, solidify after cooling, and can repeat the process, and can be recycled and reprocessed for reuse. The thermoplastic material mainly comprises polyolefin, polyether polyester, aromatic heterocyclic polymer and the like, wherein the molecular structure of the thermoplastic material does not have active groups, and linear intermolecular crosslinking does not occur when the thermoplastic material is heated. Thermoplastic composite materials are generally formed by injection molding of pure plastics, and often have poor mechanical properties. Chinese patent CN106751091a discloses a thermoplastic composite material and a method for preparing the same, comprising the steps of: mixing the corn stalk fiber powder with the auxiliary agent, and then adding recycled polystyrene, recycled high-density polyethylene and 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, corn straw fiber powder is added, so that the thermoplastic composite material has environmental protection, but the toughness and ageing resistance of the thermoplastic composite material are 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 following technical scheme:
a preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, flame-retardant filler, toughening agent, compatibilizer and antioxidant in a mass ratio of (95-115) (8-13) (10-16) (4-8) (2-5), pre-mixing for 30-40min under the process conditions of heating temperature of 185-195 ℃, loading pressure of 12-15MPa and stirring speed of 85-110rpm, and extruding and molding at 185-195 ℃ under the pressure of 2-5MPa to obtain the thermoplastic composite material.
The thermoplastic composite material obtained by remelting and casting the recycled second-hand waste thermoplastic plastic often has the problem of poor mechanical properties such as tensile strength, bending strength, impact strength and the like, so that improvement is required by optimizing a processing technology, 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, macroscopically exhibits a significant improvement in indexes including tensile, impact strength, etc., and also exhibits good resistance to ultraviolet aging.
The thermoplastic material is at least one of polyethylene plastic, polypropylene plastic, polyvinyl chloride plastic, polycarbonate plastic, polystyrene plastic and polyamide plastic.
In a preferred 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, polyethylene plastic, molecular weight: 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 plastics are all recovered second-hand waste plastics.
The compatibilizer is at least one of polytetrahydrofuran, coco fatty acid diacetyl amide and dimethyl 1, 4-cyclohexanedicarboxylate.
In a preferred scheme, the compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic 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-hydroxy anisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol).
In a preferred embodiment, 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): (0.1-1.5): (1-4.2).
The preparation method of the flame-retardant filler comprises the following steps:
mixing the regenerated carbon fiber with 30-70wt% acetone water solution according to a mass ratio of 1 (5-10), and performing ultrasonic treatment for 0.5-1h under the conditions of 20-30kHz and 200-350W of power; adding nitric acid with the concentration of 7-10mol/L, which is 100-200% of the mass 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 70-80deg.C for 3-5 hr; calcining at 500-600 deg.c for 3-5 hr to obtain pretreated carbon fiber; mixing isopropyl distearoyl oxy aluminate, gamma-glycidyl ether oxypropyl trimethoxy silane, 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 1-3 hours, filtering, washing with isopropanol, and drying at 70-90 ℃ for 1-3 hours to obtain the flame retardant filler.
Wherein, the regenerated carbon fiber is recovered from waste carbon fiber reinforced composite material (CFRP) after mechanical rolling and chemical treatment, and the fiber length 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 ultra-high pressure treatment for 23-28min under the pressure of 530-540MPa to obtain starch paste;
A2, adding hydrochloric acid with the concentration of 1.5-2mol/L and the mass of 5-6.3% into the starch paste, and then treating for 18-22min by microwaves with the frequency of 475-480MHz and the power of 480-500W to obtain acidified starch paste;
a3, stirring at 20-25rpm for 25-35min under the water bath heating state with the temperature of 60-62 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1 (6.5-8);
a4, respectively adding 12-15% of lecithin and 5-7% of oleamide into the zein solution, and performing ultrasonic treatment at 57-60 ℃ for 30-40min at the frequency of 41-43kHz and the power of 330-350W 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) (45-49), and then putting the mixture into a reaction kettle to react for 70-90min according to the technological parameters of 126-130 ℃ and 16-18.5MPa of pressure and 10-30rpm of stirring speed to obtain an intermediate product C;
a6, cooling to 65-70 ℃, adding 3-methylbenzoic acid barium salt accounting for 3-5% of the mass of the intermediate product C, performing ultrasonic treatment for 30-40min at the frequency of 39-40kHz and the power of 320-330W, cooling to 4-7 ℃, standing at the temperature for 160-200min, centrifuging at the speed of 7000-8000rpm for 3-6min, and taking a precipitate B;
A7, decompressing and drying the sediment B according to the technological parameters of 68-70 ℃, 3-6kPa, 10-30rpm of stirring speed and 130-170min of drying time to obtain the toughening agent.
Corn starch has wide sources and low price, and often has various good special performances after various modification treatments. The ultrahigh pressure treatment can cause the crystallization configuration of the corn starch to be destroyed and recombined, thereby changing the rheological property and pasting dynamics of the corn starch, and after a part of hydrogen bonds in the corn starch are destroyed, active branched chains with higher free energy are formed in an acidic environment, so that the acidified starch paste can be fully grafted and crosslinked with modified zein, polyethylenimine and isocyanate in a subsequent anisole environment, and a toughening agent with high toughness and strong adhesive force is obtained. In addition, 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 guidance of active branched chains of the acidified starch molecules, and the thermoplastic composite material has an isotropic microstructure, so that the microstructure with high unified approximation brings more macroscopic properties of impact resistance, stretching resistance, compression resistance and shearing resistance.
Zein has alpha-helices and beta-sheets with amino-terminal-NH 2 And carboxyl-COOH, also in rod-like molecular configuration and rich side chains, such molecular characteristics make it have good binding ability and oxygen-and wear-and grease-resistant properties. 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 space three-dimensional molecular structure with stronger elasticity is obtained, which benefits from strong nonpolar affinity among the lecithin, oleamide and zein. And, oleamide also has scratch resistance, offset resistance, abrasion resistance, and can enhance durability of the resulting thermoplastic composite.
The polyimide has strong adhesive force and can strengthen the connection strength between various thermoplastic materials. The modified zein also has good compatibility with the nitrogen atom-containing polyacetylimine due to the nitrogen-containing group of the oleamide.
According to the invention, the flocculent intermediate product is precipitated by utilizing the barium 3-methylbenzoate, so that the toughening agent is obtained, and the barium element contained in the toughening agent can be synergistically synergistic with 4,4' -thiobis (6-tert-butyl-2-methylphenol) in the adopted compound antioxidant, so that the electron cloud energy state distribution between the toughening agent and the compound antioxidant is beneficial to timely extinguishing free radicals with oxidative destruction capability generated by ultraviolet excitation.
The isocyanate is at least one of diphenylmethane diisocyanate and benzoyl isothiocyanate.
The isocyanate has unsaturated bond in molecular structure, thus has higher reactivity, and can easily react with some organic matters with active groups to generate polyurethane elastomer, and the elastomer can make a considerable contribution to the elasticity of the whole material. A portion of the hydroxyl groups contained in the acidified starch paste may form aminomethyl acid esters with isocyanates; the amino group in the modified zein can form urea with isocyanate, and the urea can provide certain oxidation resistance and corrosion resistance for the whole material.
A preferred embodiment is that the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in the mass ratio of (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, and the overall connection strength of the material is enhanced, and the mechanical strength including tensile impact strength is improved macroscopically; in addition to the improvement of the compatibility contributed by the nonpolar groups, the benzoyl isothiocyanate can generate hydrogen bonds between sulfur elements at specific sites contained in the benzoyl isothiocyanate and sulfur bonds in the modified zein, so that the bonding strength between the raw materials in the toughening agent is enhanced, the degree of mismatching of each phase in the whole material is reduced, the microstructure of the material is enabled to be higher isotropy, and the mechanical strength including tensile impact strength of the material is enabled to be obviously improved macroscopically, so that the material has good toughness and strength.
A more preferred scheme is that the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in a mass ratio of 2:1.
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, and the strength and the oxidation resistance are presumably related to the synergistic reduction of the mismatching degree caused by the difference of the molecular weight of the two isocyanates, and the combination of the two materials reduces the free energy of the whole material, so that the material shows more stable properties.
The invention has the beneficial effects that: the thermoplastic composite material is prepared by extrusion molding after the thermoplastic material, the flame retardant filler, the toughening agent, the compatibilizer and the antioxidant are subjected to heating, pressurizing and pre-mixing treatment, and has good mechanical properties such as tensile impact strength, good flame retardant property and ageing resistance. The toughening agent added in the raw material formula is prepared from acidified starch paste, modified zein, polyethyleneimine, isocyanate and anisole serving as raw materials, so that isotropy of a microstructure of the thermoplastic composite material can be remarkably improved, and macroscopic mechanical strength improvement can be obtained.
Detailed Description
The above summary of the application is described in further detail below in connection with the detailed description, but it should not be construed that the scope of the above subject matter of the application is limited to the examples described below.
Introduction of partial raw materials in the application:
corn starch, CAS:9005-25-8, jinan Fugang chemical Co., ltd., product number: XFV0809 and 0809.
Zein, CAS:9010-66-6, siamprenes Bioengineering Co., ltd., product number: 232.
lecithin, CAS:8002-43-5, hebei Runfu Biotechnology Co., ltd., product number: l20-03.
Polyethyleneimine, CAS:9002-98-6, molecular weight: 1 ten thousand, shandong Liang New Material science and technology Co., ltd., model: LA-7Q.
Diphenylmethane diisocyanate, CAS:5101-68-8.
Benzoyl isothiocyanate, CAS:532-55-8.
Polytetrahydrofuran, CAS:24979-97-3, molecular weight: 1000, hubei Jiujiu Feng Longhua company, inc., product number: 00084.
coco fatty acid diacetamide, 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.
Copolymers of styrene and maleic anhydride, CAS:9011-13-6, molecular weight: 2 ten thousand, shanghai Michel chemical technologies Co.
Example 1
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The toughening agent is a copolymer of styrene and maleic anhydride.
Example 2
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1:7;
A2, respectively adding 15% of lecithin and 7% of oleamide into the zein solution, and performing ultrasonic treatment at 60 ℃ for 40min at a frequency of 43kHz and a power of 350W to obtain modified zein;
a3, mixing modified zein, polyethylenimine, isocyanate and anisole according to a mass ratio of 15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80min according to technological parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is benzoyl isothiocyanate;
a4, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a5, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 3
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, heating to 95 ℃ and stirring at a rotating speed of 30rpm for 50min to obtain starch paste;
a2, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1:7;
a3, respectively adding 15% of lecithin and 7% of oleamide into the zein solution, and performing ultrasonic treatment at 60 ℃ for 40min at a frequency of 43kHz and a power of 350W to obtain modified zein;
a4, mixing the starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole according to a mass ratio of 18:15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the process parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is benzoyl isothiocyanate;
A5, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a6, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 4
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, treating for 25min by using ultra-high pressure with a size of 540MPa, and treating for 20min by using microwaves with a frequency of 480MHz and a power of 500W to obtain starch paste;
a2, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1:7;
a3, respectively adding 15% of lecithin and 7% of oleamide into the zein solution, and performing ultrasonic treatment at 60 ℃ for 40min at a frequency of 43kHz and a power of 350W to obtain modified zein;
a4, mixing the starch paste, the modified zein, the polyethyleneimine, the isocyanate and the anisole according to a mass ratio of 18:15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the process parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is benzoyl isothiocyanate;
A5, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a6, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 5
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, and performing ultra-high pressure treatment for 25min under the pressure of 540MPa to obtain starch paste;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass percentage of 6% into the starch paste, and then treating for 20min by microwaves with the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, mixing the acidified starch paste, the polyethylenimine, the isocyanate and the anisole according to a mass ratio of 18:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the technological parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is benzoyl isothiocyanate;
a4, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a5, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 6
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, and performing ultra-high pressure treatment for 25min under the pressure of 540MPa to obtain starch paste;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass percentage of 6% into the starch paste, and then treating for 20min by microwaves with the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
A3, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide; the mass ratio of zein to dimethyl sulfoxide is 1:7; then ultrasonic treatment is carried out for 40min at 60 ℃ with the frequency of 43kHz and the power of 350W to obtain zein solution;
a4, mixing the acidified starch paste, the zein solution, the polyethyleneimine, the isocyanate and the anisole according to the mass ratio of 18:15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the technological parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is benzoyl isothiocyanate;
a5, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a6, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 7
A preparation method of a thermoplastic composite material comprises the following steps:
Mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
The antioxidant is a mixture of 2, 4-di-tert-butylphenol and tert-butyl p-hydroxy anisole in a mass ratio of 2:1.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, and performing ultra-high pressure treatment for 25min under the pressure of 540MPa to obtain starch paste;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass percentage of 6% into the starch paste, and then treating for 20min by microwaves with the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1:7;
A4, respectively adding 15% of lecithin and 7% of oleamide into the zein solution, and performing ultrasonic treatment at 60 ℃ for 40min at a frequency of 43kHz and a 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 the mass ratio of 18:15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the technological parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is benzoyl isothiocyanate;
a6, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a7, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 8
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, and performing ultra-high pressure treatment for 25min under the pressure of 540MPa to obtain starch paste;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass percentage of 6% into the starch paste, and then treating for 20min by microwaves with the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1:7;
a4, respectively adding 15% of lecithin and 7% of oleamide into the zein solution, and performing ultrasonic treatment at 60 ℃ for 40min at a frequency of 43kHz and a 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 the mass ratio of 18:15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the technological parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is diphenylmethane diisocyanate;
a6, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a7, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 9
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, and performing ultra-high pressure treatment for 25min under the pressure of 540MPa to obtain starch paste;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass percentage of 6% into the starch paste, and then treating for 20min by microwaves with the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1:7;
a4, respectively adding 15% of lecithin and 7% of oleamide into the zein solution, and performing ultrasonic treatment at 60 ℃ for 40min at a frequency of 43kHz and a 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 the mass ratio of 18:15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the technological parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is benzoyl isothiocyanate;
a6, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a7, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 10
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, toughening agent, compatibilizer and antioxidant in a mass ratio of 102:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, and performing ultra-high pressure treatment for 25min under the pressure of 540MPa to obtain starch paste;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass percentage of 6% into the starch paste, and then treating for 20min by microwaves with the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1:7;
a4, respectively adding 15% of lecithin and 7% of oleamide into the zein solution, and performing ultrasonic treatment at 60 ℃ for 40min at a frequency of 43kHz and a 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 the mass ratio of 18:15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the technological parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in a mass ratio of 2:1;
a6, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a7, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 3kPa of pressure, 20rpm of stirring speed and 150min of drying time to obtain the toughening agent.
Example 11
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, flame-retardant filler, toughening agent, compatibilizer and antioxidant according to the mass ratio of 102:12:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, and performing ultra-high pressure treatment for 25min under the pressure of 540MPa to obtain starch paste;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass percentage of 6% into the starch paste, and then treating for 20min by microwaves with the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
a3, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1:7;
a4, respectively adding 15% of lecithin and 7% of oleamide into the zein solution, and performing ultrasonic treatment at 60 ℃ for 40min at a frequency of 43kHz and a 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 the mass ratio of 18:15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the technological parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in a mass ratio of 2:1;
a6, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a7, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 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-glycidoxypropyl trimethoxysilane, regenerated carbon fiber and isopropanol according to a mass ratio of 2.5:15:65, stirring for 1.5h at 65 ℃ and 300rpm, filtering, washing with isopropanol for 3 times, and drying for 2h at 85 ℃ 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 and the oxygen index thereof was 28.7%.
Example 12
A preparation method of a thermoplastic composite material comprises the following steps:
mixing thermoplastic material, flame-retardant filler, toughening agent, compatibilizer and antioxidant according to the mass ratio of 102:12:14:6:4, pre-mixing for 35min under the process conditions of 190 ℃ of heating temperature, 14MPa of loading pressure and 100rpm of stirring speed, and 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 2:2:1.
The compatibilizer is a mixture of polytetrahydrofuran, coco fatty acid diacetyl amide and 1, 4-cyclohexanedicarboxylic acid dimethyl ester in a mass ratio of 3:1:2.
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 2:1:2.
The preparation method of the toughening agent comprises the following steps:
a1, mixing corn starch and water according to a mass ratio of 1:4, and performing ultra-high pressure treatment for 25min under the pressure of 540MPa to obtain starch paste;
a2, adding hydrochloric acid with the concentration of 2mol/L and the mass percentage of 6% into the starch paste, and then treating for 20min by microwaves with the frequency of 480MHz and the power of 500W to obtain acidified starch paste;
A3, stirring at 25rpm for 30min under the water bath heating state with the temperature of 60 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1:7;
a4, respectively adding 15% of lecithin and 7% of oleamide into the zein solution, and performing ultrasonic treatment at 60 ℃ for 40min at a frequency of 43kHz and a 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 the mass ratio of 18:15:10:4:46, then putting the mixture into a reaction kettle, and reacting for 80 minutes according to the technological parameters of 127 ℃ and 17.5MPa of pressure and 20rpm of stirring speed to obtain an intermediate product C; the isocyanate is a mixture of diphenylmethane diisocyanate and benzoyl isothiocyanate in a mass ratio of 2:1;
a6, cooling to 70 ℃, adding 4% of 3-barium methylbenzoate by mass 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, and centrifuging for 5min at the speed of 8000rpm to obtain a precipitate B;
a7, decompressing and drying the sediment B according to the technological parameters of 70 ℃ and 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 60wt% acetone aqueous solution at a mass ratio of 1:8, and performing ultrasonic treatment for 0.5h under the conditions of 25kHz and 300W of power; adding nitric acid with the concentration of 8.5mol/L, which is 150% of the mass of the regenerated carbon fiber, and continuing ultrasonic treatment at 78 ℃ for 1.5h; filtering, washing with water to neutrality, and oven drying at 80deg.C for 3 hr; then placing the mixture at 600 ℃ for calcination for 3.5 hours to obtain pretreated carbon fibers; mixing isopropyl distearoyl oxyaluminate, gamma-glycidyl ether oxypropyl trimethoxy silane, pretreated carbon fiber and isopropanol in a mass ratio of 1:1.5:15:65, stirring for 1.5h at 65 ℃ and 300rpm, 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 12 were determined with reference to GB/T2406.2-2009 and the oxygen index was 34.2%.
Test example 1
Tensile impact test: the tensile impact strength of the thermoplastic composites obtained by the examples of the invention was determined according to GB/T13525-1992 method for testing tensile impact properties of plastics. The test adopts a B-type sample; the thickness of the sample is 1mm; 10 different samples were selected for each example and the test results averaged.
TABLE 1 tensile impact Strength of thermoplastic composites
Test example 2
Ultraviolet resistance aging test: first, according to GB/T16422.3-2014, section 3 of the Plastic laboratory light Source Exposure test method: method A in fluorescent UV Lamp the thermoplastic composites obtained from inventive example 1 and examples 7-10 were aged irradiated. The test environment was at 23℃and 40% relative humidity, and UV aging irradiation treatment was performed using a type 1A (UVA-340) fluorescent UV lamp. Then, the yellowing index DeltaYI of the above-mentioned ultraviolet aging-irradiated sample was measured according to HG/T3862-2006 "test method for Plastic yellow index". The ultraviolet aging data of 10 different samples were tested in each example and the test results were averaged.
TABLE 2 UV aging resistance of thermoplastic composites
The traditional thermoplastic plastics have the problem of poor toughness, and are particularly low in mechanical indexes such as tensile strength, bending strength, shearing strength and the like. In the field of reclaimed plastics, various second-hand thermoplastics are often subjected to simple remelting and recasting, and the obtained simple polymer often has poor mechanical strength, poor tensile, compressive and bending resistance and even often cannot meet the standard of normal use. With the awareness of energy consumption and environmental awareness, there is an increasing need in the market for a thermoplastic material production process that can improve the toughness strength of thermoplastic materials and also has a significant strength improving effect on recycled plastics. Therefore, the invention aims to provide a preparation method of the thermoplastic composite material, which not only can improve the toughness strength of the thermoplastic material, but also has a remarkable strength improving effect on the recycled plastic. The method has the advantages of simple process, safety, environmental protection, high efficiency and low cost, and the obtained thermoplastic composite material has an isotropic microstructure, is macroscopically shown to have obviously improved toughness strength indexes including tensile impact strength and the like, and also has good ultraviolet aging resistance. Corn starch has wide sources and low price, and often has various good special performances after various modification treatments. The ultrahigh pressure treatment can cause the crystallization configuration of the corn starch to be destroyed and recombined, thereby changing the rheological property and pasting dynamics of the corn starch, and after a part of hydrogen bonds in the corn starch are destroyed, active branched chains with higher free energy are formed in an acidic environment, so that the acidified starch paste can be fully grafted and crosslinked with modified zein, polyethylenimine and isocyanate in a subsequent anisole environment, and a toughening agent with high toughness and strong adhesive force 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 acidified starch molecules under the guidance of active branched chains of the acidified starch molecules The thermoplastic composite material has isotropic microstructure, so that the microstructure with high unified approximation brings more macroscopic properties of impact resistance, stretching resistance, compression resistance and shearing resistance. Zein has alpha-helices and beta-sheets with amino-terminal-NH 2 And carboxyl-COOH, also in rod-like molecular configuration and rich side chains, such molecular characteristics make it have good binding ability and oxygen-and wear-and grease-resistant properties. 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 space three-dimensional molecular structure with stronger elasticity is obtained, which benefits from strong nonpolar affinity among the lecithin, oleamide and zein. In addition, the oleamide also has scratch resistance, offset resistance and abrasion resistance, and can enhance the durability of the obtained thermoplastic composite material. The polyimide has strong adhesive force and can strengthen the connection strength between various thermoplastic materials. The modified zein also has good compatibility with the nitrogen atom-containing polyacetylimine due to the nitrogen-containing group of the oleamide. The isocyanate has unsaturated bond in molecular structure, thus has higher reactivity, and can easily react with some organic matters with active groups to generate polyurethane elastomer, and the elastomer can make a considerable contribution to the elasticity of the whole material. A portion of the hydroxyl groups contained in the acidified starch paste may form aminomethyl acid esters with isocyanates; the amino group in the modified zein can form urea with isocyanate, and the urea can provide certain oxidation resistance and corrosion resistance for the whole material. Wherein 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, and the overall connection strength of the material is enhanced, and the macroscopic mechanical strength including tensile impact strength is improved; in addition to the enhanced compatibility contributed by the nonpolar groups, the benzoyl isothiocyanate can also generate hydrogen bonds between sulfur elements at specific sites and sulfur bonds in the modified zein, thereby enhancing the toughening agent The bonding strength between the raw materials also reduces the degree of mismatching of each phase in the overall material, so that the microstructure of the material shows higher isotropy, and the material is macroscopically shown to be remarkably improved in mechanical strength including tensile impact strength, and 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, and the strength and the oxidation resistance are presumably related to the synergistic reduction of the mismatching degree caused by the difference of the molecular weight of the two isocyanates, and the combination of the two materials reduces the free energy of the whole material, so that the material shows more stable properties. According to the invention, the flocculent intermediate product is precipitated by utilizing the barium 3-methylbenzoate, so that the toughening agent is obtained, and the barium element contained in the toughening agent can be synergistically synergistic with 4,4' -thiobis (6-tert-butyl-2-methylphenol) in the adopted compound antioxidant, so that the electron cloud energy state distribution between the toughening agent and the compound antioxidant is beneficial to timely extinguishing free radicals with oxidative destruction capability generated by ultraviolet excitation.
Claims (6)
1. A method for preparing a thermoplastic composite material, comprising the steps of:
Mixing thermoplastic material, flame-retardant filler, toughening agent, compatibilizer and antioxidant in a mass ratio of (95-115) (8-13) (10-16) (4-8) (2-5), pre-mixing for 30-40min under the process conditions of heating temperature of 185-195 ℃, loading pressure of 12-15MPa and stirring speed of 85-110rpm, and extruding and forming at 185-195 ℃ under the pressure of 2-5MPa to obtain the thermoplastic composite material;
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 ultra-high pressure treatment for 23-28min under the pressure of 530-540MPa to obtain starch paste;
a2, adding hydrochloric acid with the concentration of 1.5-2mol/L and the mass of 5-6.3% into the starch paste, and then treating for 18-22min by microwaves with the frequency of 475-480MHz and the power of 480-500W to obtain acidified starch paste;
a3, stirring at 20-25rpm for 25-35min under the water bath heating state with the temperature of 60-62 ℃ to dissolve zein in dimethyl sulfoxide to obtain zein solution; the mass ratio of zein to dimethyl sulfoxide is 1 (6.5-8);
a4, respectively adding 12-15% of lecithin and 5-7% of oleamide into the zein solution, and performing ultrasonic treatment at 57-60 ℃ for 30-40min at the frequency of 41-43kHz and the power of 330-350W 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) (45-49), and then putting the mixture into a reaction kettle to react for 70-90min according to the technological parameters of 126-130 ℃ and 16-18.5MPa of pressure and 10-30rpm of stirring speed to obtain an intermediate product C;
a6, cooling to 65-70 ℃, adding 3-methylbenzoic acid barium salt accounting for 3-5% of the mass of the intermediate product C, performing ultrasonic treatment for 30-40min at the frequency of 39-40kHz and the power of 320-330W, cooling to 4-7 ℃, standing at the temperature for 160-200min, centrifuging at the speed of 7000-8000rpm for 3-6min, and taking a precipitate B;
a7, decompressing and drying the sediment B by using technological parameters with the temperature of 68-70 ℃, the pressure of 3-6kPa, the stirring speed of 10-30rpm and the drying time of 130-170min to obtain the toughening agent;
the isocyanate is at least one of diphenylmethane diisocyanate and benzoyl isothiocyanate.
2. The method of preparing a thermoplastic composite material according to claim 1, wherein the method of preparing the flame retardant filler comprises:
mixing the regenerated carbon fiber with 30-70wt% acetone water solution according to a mass ratio of 1 (5-10), and performing ultrasonic treatment for 0.5-1h under the conditions of 20-30kHz and 200-350W of power; adding nitric acid with the concentration of 7-10mol/L, which is 100-200% of the mass 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 70-80deg.C for 3-5 hr; calcining at 500-600 deg.c for 3-5 hr to obtain pretreated carbon fiber; mixing isopropyl distearoyl oxy aluminate, gamma-glycidyl ether oxypropyl trimethoxy silane, 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 1-3 hours, filtering, washing with isopropanol, and drying at 70-90 ℃ for 1-3 hours to obtain the flame retardant filler.
3. A method of preparing a thermoplastic composite material as claimed in 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 preparing a thermoplastic composite material as claimed in claim 1, wherein: the compatibilizer is at least one of polytetrahydrofuran, coco fatty acid diacetyl amide and dimethyl 1, 4-cyclohexanedicarboxylate.
5. A method of preparing a thermoplastic composite material as claimed in claim 1, wherein: the antioxidant is at least one of 2, 4-di-tert-butylphenol, tert-butyl p-hydroxy anisole and 4,4' -thiobis (6-tert-butyl-2-methylphenol).
6. A thermoplastic composite material characterized by: obtained by the production process according to any one of claims 1 to 5.
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| CN102181140A (en) * | 2011-03-24 | 2011-09-14 | 北京化工大学 | Carbon fiber silk waste reinforced polycarbonate composite material and preparation method of the carbon fiber silk waste reinforced polycarbonate composite material |
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| CN112457575A (en) * | 2020-10-27 | 2021-03-09 | 东莞市鑫塑源塑胶科技有限公司 | Polypropylene halogen-free flame-retardant material and preparation method thereof |
| WO2022173073A1 (en) * | 2021-02-15 | 2022-08-18 | 대상 주식회사 | Thermoplastic starch composition, method for preparing same, and uses thereof |
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