CN112210166A - High-strength scratch-resistant wollastonite modified polypropylene plastic composite material and preparation method thereof - Google Patents
High-strength scratch-resistant wollastonite modified polypropylene plastic composite material and preparation method thereof Download PDFInfo
- Publication number
- CN112210166A CN112210166A CN202011082236.6A CN202011082236A CN112210166A CN 112210166 A CN112210166 A CN 112210166A CN 202011082236 A CN202011082236 A CN 202011082236A CN 112210166 A CN112210166 A CN 112210166A
- Authority
- CN
- China
- Prior art keywords
- wollastonite
- composite material
- resistant
- plastic composite
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the technical field of plastics and discloses a high-strength scratch-resistant wollastonite modified polypropylene plastic composite material and a preparation method thereof. The polypropylene plastic composite material comprises the following components in parts by weight: 70-80 parts of polypropylene, 10-20 parts of metal organic framework wollastonite composite particles, 0.2-0.5 part of organic phosphate nucleating agent, 0.1-0.3 part of antioxidant and 0.1-0.3 part of light stabilizer; adding the polypropylene and metal organic frame wollastonite composite particles into a stirrer, stirring at normal temperature, adding the organic phosphate nucleating agent, the antioxidant and the light stabilizer, continuously stirring to obtain a mixture, adding the mixture into a screw extruder, and performing melt extrusion and granulation to obtain the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material. The polypropylene plastic composite material prepared by the invention has excellent mechanical property and scratch resistance.
Description
Technical Field
The invention relates to the field of plastics, in particular to a high-strength scratch-resistant wollastonite modified polypropylene plastic composite material and a preparation method thereof.
Background
The polypropylene is one of the most used general plastics at present, and the density of the polypropylene is 0.89-0.91g/cm3Because of the advantages of small density, low price, excellent electrical insulation, innocuity, corrosion resistance, easy processing and the like, the composite material is widely applied to the industries of chemical industry, machinery, transportation and the like. In which poly is collectedThe application of propylene in automobiles becomes one of the main research directions for the localization of parts in the automobile industry in China, and polypropylene materials are mainly applied to automobile components such as automobile door panels, instrument panels, decorative columns and the like. However, scratches are inevitably generated on the plastic shell in the production, storage, transportation and use processes of the product, which affects the aesthetic property and the service performance of the product, and shortens the service life of the polypropylene material.
Chinese patent publication No. CN101759920 discloses a polypropylene composite material with improved scratch resistance and a preparation method thereof, which comprises polypropylene, an antioxidant, a light stabilizer and other auxiliary agents; according to the technical scheme, the scratch resistance of the material is improved on the basis of improving the mechanical property of the material by adding the wollastonite as an inorganic filler in the formula. However, the interface bonding capability between the organic material polypropylene and the inorganic wollastonite is poor, and the wollastonite is not uniformly dispersed in the polypropylene, so that the improvement of the mechanical property and the scraping resistance of the wollastonite on the polypropylene is influenced.
Chinese patent publication No. CN102875899 discloses a method for toughening and reinforcing modified polypropylene by wollastonite, which comprises polypropylene, polyethylene, a toughening agent, wollastonite, an auxiliary stiffening agent, a stabilizer and pigment; according to the technical scheme, the silane coupling agent and the silicone oil are compounded to modify the surface of the wollastonite, and then the dihydric alcohol and the isocyanate are coated on the surface of the wollastonite.
Chinese patent publication No. CN103131078 discloses a flame-retardant scratch-resistant polypropylene material for cabinets and a preparation method thereof, which comprises polypropylene, glass fiber, a compatilizer, a compound flame retardant and a scratch-resistant agent; the amide or high molecular weight siloxane polymer used in the technical scheme is used as the scratch resistant agent of polypropylene, but the amide low molecular weight migrates to the surface of the material to influence the odor and volatilization characteristics of the material, and the siloxane polymer high molecular compound does not easily migrate to the surface of the material, so that the ideal scratch resistant effect cannot be obtained under the condition of low addition amount.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a high-strength scratch-resistant wollastonite modified polypropylene plastic composite material. According to the invention, the metal organic framework wollastonite composite particles are added into the polypropylene material as a filler and an auxiliary agent, and the metal organic framework wollastonite composite particles and the polypropylene have good compatibility and interface bonding acting force, so that the raw material cost of the polypropylene material is reduced, and the scratch resistance and the mechanical property of the polypropylene material can be greatly improved.
The invention also provides a preparation method of the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material.
In order to achieve the purpose, the invention adopts the following technical scheme: the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following components in parts by weight:
70-80 parts of polypropylene, 10-20 parts of metal organic framework wollastonite composite particles, 0.2-0.5 part of organic phosphate nucleating agent, 0.1-0.3 part of antioxidant and 0.1-0.3 part of light stabilizer.
Preferably, the preparation method of the metal organic framework wollastonite composite particle comprises the following steps:
adding zinc nitrate hexahydrate into a methanol solution, stirring and dissolving to obtain a zinc nitrate solution, adding wollastonite and sodium bicarbonate into the zinc nitrate solution, and uniformly dispersing by ultrasonic oscillation to obtain a suspension; adding 2-methylimidazole into a methanol solution, stirring and dissolving to obtain a 2-methylimidazole solution, adding the 2-methylimidazole solution into the suspension, mixing and stirring for 2-5h, carrying out suction filtration, and drying in an oven at 60-70 ℃ for 1-3h to obtain the metal organic framework wollastonite composite particles.
According to the invention, needle-shaped wollastonite is added into polypropylene, and the wollastonite is used as a filler and a functional assistant of polypropylene plastic, so that the cost of raw materials is reduced, and the scraping resistance and the mechanical strength of the polypropylene plastic are improved. Because polypropylene is an organic polymer and wollastonite enables inorganic particles to have poor compatibility and interface bonding capability, the wollastonite is not uniformly dispersed in polypropylene plastics, and the improvement of the wollastonite on the mechanical properties of the polypropylene plastics is reduced. The wollastonite is modified, zinc ions and 2-methylimidazole are utilized to synthesize metal organic framework nano particles through self-assembly, the metal organic framework nano particles have molecular inner holes formed by assembling a large number of organic ligands or clusters, the surface of the metal organic framework nano particles presents a porous structure, the metal organic framework nano particles are deposited and combined on the surfaces of the needle-shaped wollastonite to prepare the metal organic framework wollastonite composite particles, and the metal organic framework nano particles organize the surfaces of the needle-shaped wollastonite, so that the compatibility between the wollastonite and polypropylene is improved, the dispersion performance of the wollastonite in the polypropylene is improved, the mechanical property of the wollastonite to the polypropylene plastic is improved, and the scraping resistance and the mechanical strength of the polypropylene plastic are improved. On the other hand, the metal organic framework particles combined on the surface of the wollastonite are of a porous structure, and polypropylene molecular chains are diffused into the porous structure of the metal organic framework wollastonite composite particles in the blending and melting process of the polypropylene and the metal organic framework wollastonite composite particles, so that the combination acting force between the polypropylene and the wollastonite is improved, and the mechanical strength of the polypropylene plastic is further improved. In the experiment, the research finds that sodium bicarbonate is added in the process of synthesizing the metal organic framework nano particles by self-assembly of zinc ions and 2-methylimidazole, and the sodium bicarbonate generates carbon dioxide gas to overflow when being heated subsequently, so that the pore size of the surface of the metal organic framework nano particles is improved, the polypropylene molecular chain is favorably diffused into the porous structure of the metal organic framework wollastonite composite particles, and the diffusion of the polypropylene molecular chain into the porous structure of the metal organic framework wollastonite composite particles is difficult due to the small surface pore size of the metal organic framework nano particles which are not assembled and synthesized by adding the sodium bicarbonate, so that the improvement of the mechanical strength of polypropylene plastics is limited.
Preferably, the mass ratio of the wollastonite to the zinc nitrate hexahydrate is 1: 0.3-0.6.
Preferably, the mixing mass ratio of the zinc nitrate hexahydrate to the 2-methylimidazole is 1: 5-10.
Preferably, the step 1) of pretreating the wollastonite comprises the following steps:
adding wollastonite into a hydrochloric acid solution for soaking, performing suction filtration and water washing, and then placing the wollastonite in an oven for drying to obtain hydrochloric acid-treated wollastonite; adding an epoxy silane coupling agent into a mixed solution of ethanol and water, uniformly stirring and mixing, adjusting the pH of the system to 3-5, adding wollastonite treated by hydrochloric acid into the mixed solution, heating in a water bath to 50-60 ℃, stirring and reacting for 1-3h, and performing suction filtration, washing and drying to obtain silane coupling agent modified wollastonite; adding carboxymethyl chitosan into deionized water, stirring and dissolving to prepare a carboxymethyl chitosan solution, adding silane coupling agent modified wollastonite into the carboxymethyl chitosan solution, then adding a tin tetrachloride catalyst, heating in a water bath to 70-80 ℃, stirring and reacting for 2-5h, and performing suction filtration, washing and drying to obtain the carboxymethyl chitosan modified wollastonite.
In the subsequent preparation process of the polypropylene plastic composite material, the mixture of the polypropylene and the metal organic framework wollastonite composite particles is added into a screw extruder for melt mixing, and experiments show that a large amount of metal organic framework nano particles combined with the surface of the wollastonite fall off from the surface of the wollastonite under the condition of high-temperature melt pressure mixing, so that the improvement of the mechanical property of the polypropylene plastic by the wollastonite is influenced. Therefore, the invention further pretreats wollastonite to improve the scraping resistance and the mechanical strength of polypropylene plastics, the surface of needle-shaped wollastonite is subjected to acid etching treatment by hydrochloric acid to obtain wollastonite with a pit shape on the surface, then the surface of the wollastonite is grafted with an epoxy silane coupling agent to load epoxy groups, and then the epoxy groups on the surface of the wollastonite and hydroxyl groups on carboxymethyl chitosan molecules are subjected to ring opening reaction to graft carboxymethyl chitosan on the surface of the wollastonite. Zinc ions and 2-methylimidazole are synthesized into metal organic framework nano particles through self-assembly and deposited and combined in the pits on the surface of the needle-shaped wollastonite, and carboxyl groups in carboxymethyl chitosan molecules grafted on the surface of the wollastonite and the zinc ions on the metal organic framework nano particles interact to form coordination bonds, so that the metal organic framework nano particles are stably combined on the surface of the needle-shaped wollastonite, the metal organic framework nano particles combined on the surface of the wollastonite are prevented from falling off from the surface of the wollastonite in the process of melt blending of polypropylene and the needle-shaped wollastonite, and the scratch resistance and the mechanical property of the wollastonite to polypropylene plastics are improved.
Preferably, the mass concentration of the hydrochloric acid solution is 0.5 to 1.0%.
Preferably, the mass ratio of the hydrochloric acid-treated wollastonite to the epoxy silane coupling agent is 1:0.2 to 0.5.
Preferably, the mass ratio of the silane coupling agent modified wollastonite to the carboxymethyl chitosan is 1: 0.5-1.
The preparation method of the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following steps:
adding the polypropylene and metal organic frame wollastonite composite particles into a stirrer, stirring for 10-20min at normal temperature, then adding the organic phosphate nucleating agent, the antioxidant and the light stabilizer, continuing stirring for 20-30min to obtain a mixture, adding the mixture into a screw extruder, and performing melt extrusion and granulation to obtain the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material.
Preferably, the extrusion temperature of the screw extruder is controlled at 180-220 ℃.
Therefore, the invention has the following beneficial effects: (1) zinc ions and 2-methylimidazole are utilized to synthesize metal organic framework nano particles through self-assembly, the metal organic framework nano particles are deposited and combined on the surfaces of the needle-shaped wollastonite to prepare metal organic framework wollastonite composite particles, and the metal organic framework nano particles organize the surfaces of the needle-shaped wollastonite, so that the compatibility between the wollastonite and polypropylene is improved, the dispersion performance of the wollastonite in the polypropylene is improved, the mechanical property of the wollastonite to polypropylene plastic is improved, and the scraping resistance and the mechanical strength of the polypropylene plastic are improved; (2) the metal organic frame nano particles are stably combined on the surface of the needle-shaped wollastonite, so that the metal organic frame nano particles combined on the surface of the wollastonite are prevented from falling off from the surface of the wollastonite in the process of melt blending of polypropylene and the needle-shaped wollastonite, and the scratch resistance and the mechanical property of the wollastonite to polypropylene plastics are improved.
Drawings
FIG. 1 is a microscopic scanning electron microscope image of a cross section of the polypropylene plastic composite material in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. The raw materials used in the present invention may be commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
The polypropylene used in the specific embodiment is isotactic polypropylene produced by Shandong Oriental Macro-Industrial chemical Co., Ltd, the melt index of the isotactic polypropylene is 5-30g/10min, and the isotactic index is more than or equal to 98.5%; the used wollastonite is needle-shaped powder which is produced by Hubei Von Jiashan silicon fiber limited company and does not contain metal, and the length-diameter ratio is 10:1-5: 1; the viscosity of the carboxymethyl chitosan is 10-100mpa.s, the carboxylation degree is more than or equal to 80 percent, and the water insoluble substance is less than or equal to 1.0 percent.
Example 1
The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following components in parts by weight:
73 parts of polypropylene, 18 parts of metal organic framework wollastonite composite particles, 18 parts of organic phosphate nucleating agent NA-710.3 parts, 10100.15 parts of antioxidant and 9440.15 parts of light stabilizer.
Pretreatment of wollastonite:
adding wollastonite into a hydrochloric acid solution with the mass concentration of 0.8%, soaking for 20min, performing suction filtration and water washing, and then placing in an oven for drying to obtain wollastonite treated by hydrochloric acid; uniformly mixing ethanol and water according to the volume ratio of 10:1 to obtain a mixed solution of ethanol and water, adding an epoxy silane coupling agent KH-560 into the mixed solution of ethanol and water according to the mass ratio of 1:30, uniformly stirring and mixing, adjusting the pH value of a system to 5, adding hydrochloric acid-treated wollastonite into the mixed solution, heating in a water bath to 60 ℃, stirring and reacting for 1h, and performing suction filtration, washing and drying to obtain silane coupling agent modified wollastonite; adding carboxymethyl chitosan into deionized water, stirring and dissolving to prepare a carboxymethyl chitosan solution, adding silane coupling agent modified wollastonite into the carboxymethyl chitosan solution, wherein the mass ratio of the silane coupling agent modified wollastonite to the carboxymethyl chitosan is 1:0.8, then adding a stannic chloride catalyst, wherein the addition amount of stannic chloride is 5% of the mass of the carboxymethyl chitosan, heating in a water bath to 75 ℃, stirring and reacting for 4 hours, and carrying out suction filtration, washing and drying to obtain the carboxymethyl chitosan modified wollastonite.
The preparation method of the metal organic framework wollastonite composite particle comprises the following steps:
adding zinc nitrate hexahydrate into a methanol solution, stirring and dissolving to obtain a zinc nitrate solution, adding the pretreated wollastonite and sodium bicarbonate into the zinc nitrate solution, and uniformly dispersing by ultrasonic oscillation, wherein the mass ratio of the wollastonite to the zinc nitrate hexahydrate is 1:0.5, and the addition amount of the sodium bicarbonate is 7 percent of the mass of the zinc nitrate hexahydrate to obtain a suspension; adding 2-methylimidazole into a methanol solution, stirring and dissolving to obtain a 2-methylimidazole solution, adding the 2-methylimidazole solution into the suspension, mixing and stirring for 4 hours, wherein the mixing mass ratio of zinc nitrate hexahydrate to 2-methylimidazole is 1:7, performing suction filtration, and drying in an oven at 70 ℃ for 1 hour to obtain the metal organic framework wollastonite composite particles.
The preparation method of the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following steps:
adding the polypropylene and metal organic frame wollastonite composite particles into a stirrer, stirring for 20min at normal temperature, adding the organic phosphate nucleating agent, the antioxidant and the light stabilizer, continuously stirring for 20min to obtain a mixture, adding the mixture into a screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature of the screw extruder is controlled at 220 ℃ to obtain the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material.
Example 2
The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following components in parts by weight:
78 parts of polypropylene, 12 parts of metal organic framework wollastonite composite particles, NA-710.4 parts of organic phosphate nucleating agent, 10100.2 parts of antioxidant and 9440.2 parts of light stabilizer.
Pretreatment of wollastonite:
adding wollastonite into a hydrochloric acid solution with the mass concentration of 0.8%, soaking for 20min, performing suction filtration and water washing, and then placing in an oven for drying to obtain wollastonite treated by hydrochloric acid; uniformly mixing ethanol and water according to the volume ratio of 10:1 to obtain a mixed solution of ethanol and water, adding an epoxy silane coupling agent KH-560 into the mixed solution of ethanol and water according to the mass ratio of 1:30, uniformly stirring and mixing, adjusting the pH value of a system to 3, adding hydrochloric acid-treated wollastonite into the mixed solution, heating in a water bath to 50 ℃, stirring and reacting for 3 hours, and performing suction filtration, washing and drying to obtain silane coupling agent modified wollastonite; adding carboxymethyl chitosan into deionized water, stirring and dissolving to prepare a carboxymethyl chitosan solution, adding silane coupling agent modified wollastonite into the carboxymethyl chitosan solution, wherein the mass ratio of the silane coupling agent modified wollastonite to the carboxymethyl chitosan is 1:0.6, then adding a stannic chloride catalyst, wherein the addition amount of stannic chloride is 5% of the mass of the carboxymethyl chitosan, heating in a water bath to 75 ℃, stirring and reacting for 3 hours, and carrying out suction filtration, washing and drying to obtain the carboxymethyl chitosan modified wollastonite.
The preparation method of the metal organic framework wollastonite composite particle comprises the following steps:
adding zinc nitrate hexahydrate into a methanol solution, stirring and dissolving to obtain a zinc nitrate solution, adding the pretreated wollastonite and sodium bicarbonate into the zinc nitrate solution, and uniformly dispersing by ultrasonic oscillation, wherein the mass ratio of the wollastonite to the zinc nitrate hexahydrate is 1:0.4, and the addition amount of the sodium bicarbonate is 7 percent of the mass of the zinc nitrate hexahydrate to obtain a suspension; adding 2-methylimidazole into a methanol solution, stirring and dissolving to obtain a 2-methylimidazole solution, adding the 2-methylimidazole solution into the suspension, mixing and stirring for 3 hours, wherein the mixing mass ratio of zinc nitrate hexahydrate to 2-methylimidazole is 1:6, performing suction filtration, and drying in a drying oven at 60 ℃ for 3 hours to obtain the metal organic framework wollastonite composite particles.
The preparation method of the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following steps:
adding the polypropylene and metal organic frame wollastonite composite particles into a stirrer, stirring for 10min at normal temperature, then adding the organic phosphate nucleating agent, the antioxidant and the light stabilizer, continuing stirring for 30min to obtain a mixture, adding the mixture into a screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature of the screw extruder is controlled at 180 ℃ to obtain the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material.
Example 3
The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following components in parts by weight:
70 parts of polypropylene, 20 parts of metal organic framework wollastonite composite particles, 710.2 parts of organic phosphate nucleating agent NA, 10100.1 parts of antioxidant and 9440.1 parts of light stabilizer.
Pretreatment of wollastonite:
adding wollastonite into a hydrochloric acid solution with the mass concentration of 1.0%, soaking for 20min, performing suction filtration and water washing, and then placing in an oven for drying to obtain wollastonite treated by hydrochloric acid; uniformly mixing ethanol and water according to the volume ratio of 10:1 to obtain a mixed solution of ethanol and water, adding an epoxy silane coupling agent KH-560 into the mixed solution of ethanol and water according to the mass ratio of 1:30, uniformly stirring and mixing, adjusting the pH value of a system to 4, adding hydrochloric acid-treated wollastonite into the mixed solution, heating in a water bath to 55 ℃, stirring and reacting for 2 hours, and performing suction filtration, washing and drying to obtain silane coupling agent modified wollastonite; adding carboxymethyl chitosan into deionized water, stirring and dissolving to prepare a carboxymethyl chitosan solution, adding silane coupling agent modified wollastonite into the carboxymethyl chitosan solution, wherein the mass ratio of the silane coupling agent modified wollastonite to the carboxymethyl chitosan is 1:1, then adding a stannic chloride catalyst, wherein the addition amount of stannic chloride is 5% of the mass of the carboxymethyl chitosan, heating in a water bath to 80 ℃, stirring and reacting for 5 hours, and performing suction filtration, washing and drying to obtain the carboxymethyl chitosan modified wollastonite.
The preparation method of the metal organic framework wollastonite composite particle comprises the following steps:
adding zinc nitrate hexahydrate into a methanol solution, stirring and dissolving to obtain a zinc nitrate solution, adding the pretreated wollastonite and sodium bicarbonate into the zinc nitrate solution, and uniformly dispersing by ultrasonic oscillation, wherein the mass ratio of the wollastonite to the zinc nitrate hexahydrate is 1:0.6, and the addition amount of the sodium bicarbonate is 7 percent of the mass of the zinc nitrate hexahydrate to obtain a suspension; adding 2-methylimidazole into a methanol solution, stirring and dissolving to obtain a 2-methylimidazole solution, adding the 2-methylimidazole solution into the suspension, mixing and stirring for 5 hours, wherein the mixing mass ratio of zinc nitrate hexahydrate to 2-methylimidazole is 1:10, performing suction filtration, and drying in a drying oven at 65 ℃ for 2 hours to obtain the metal organic framework wollastonite composite particles.
The preparation method of the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following steps:
adding the polypropylene and metal organic frame wollastonite composite particles into a stirrer, stirring for 15min at normal temperature, then adding the organic phosphate nucleating agent, the antioxidant and the light stabilizer, continuing stirring for 25min to obtain a mixture, adding the mixture into a screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature of the screw extruder is controlled at 200 ℃ to obtain the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material.
Example 4
The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following components in parts by weight:
80 parts of polypropylene, 10 parts of metal organic framework wollastonite composite particles, 710.5 parts of organic phosphate nucleating agent NA, 10100.3 parts of antioxidant and 9440.3 parts of light stabilizer.
Pretreatment of wollastonite:
adding wollastonite into a hydrochloric acid solution with the mass concentration of 0.5%, soaking for 20min, performing suction filtration and water washing, and then placing in an oven for drying to obtain wollastonite treated by hydrochloric acid; uniformly mixing ethanol and water according to the volume ratio of 10:1 to obtain a mixed solution of ethanol and water, adding an epoxy silane coupling agent KH-560 into the mixed solution of ethanol and water according to the mass ratio of 1:30, uniformly stirring and mixing, adjusting the pH value of a system to 4, adding hydrochloric acid-treated wollastonite into the mixed solution, heating in a water bath to 55 ℃, stirring and reacting for 2 hours, and performing suction filtration, washing and drying to obtain silane coupling agent modified wollastonite; adding carboxymethyl chitosan into deionized water, stirring and dissolving to prepare a carboxymethyl chitosan solution, adding silane coupling agent modified wollastonite into the carboxymethyl chitosan solution, wherein the mass ratio of the silane coupling agent modified wollastonite to the carboxymethyl chitosan is 1:0.5, then adding a stannic chloride catalyst, wherein the addition amount of stannic chloride is 5% of the mass of the carboxymethyl chitosan, heating in a water bath to 70 ℃, stirring and reacting for 2 hours, and carrying out suction filtration, washing and drying to obtain the carboxymethyl chitosan modified wollastonite.
The preparation method of the metal organic framework wollastonite composite particle comprises the following steps:
adding zinc nitrate hexahydrate into a methanol solution, stirring and dissolving to obtain a zinc nitrate solution, adding the pretreated wollastonite and sodium bicarbonate into the zinc nitrate solution, and uniformly dispersing by ultrasonic oscillation, wherein the mass ratio of the wollastonite to the zinc nitrate hexahydrate is 1:0.3, and the addition amount of the sodium bicarbonate is 7 percent of the mass of the zinc nitrate hexahydrate to obtain a suspension; adding 2-methylimidazole into a methanol solution, stirring and dissolving to obtain a 2-methylimidazole solution, adding the 2-methylimidazole solution into the suspension, mixing and stirring for 2 hours, wherein the mixing mass ratio of zinc nitrate hexahydrate to 2-methylimidazole is 1:5, performing suction filtration, and drying in a drying oven at 65 ℃ for 2 hours to obtain the metal organic framework wollastonite composite particles.
The preparation method of the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material comprises the following steps:
adding the polypropylene and metal organic frame wollastonite composite particles into a stirrer, stirring for 15min at normal temperature, then adding the organic phosphate nucleating agent, the antioxidant and the light stabilizer, continuing stirring for 25min to obtain a mixture, adding the mixture into a screw extruder, and performing melt extrusion and granulation, wherein the extrusion temperature of the screw extruder is controlled at 200 ℃ to obtain the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material.
Comparative example 1
Comparative example 1 differs from example 1 in that the metal organic framework wollastonite composite particles are replaced with wollastonite.
Comparative example 2
Comparative example 2 differs from example 1 in that sodium bicarbonate was not added during the preparation of the metal organic framework wollastonite composite particles.
Comparative example 3
Comparative example 3 differs from example 1 in that the wollastonite has not been pretreated.
1. Mechanical Property test
Preparing tensile and impact sample strips by injection molding, adjusting the sample strips in an environment at 23 +/-1 ℃ for 48H, performing a tensile test on each sample by using 5 dumbbell-shaped tensile sample strips on a universal material testing machine according to the GB/T1040 standard, controlling the tensile rate to be 100mm/min, preparing the impact sample strips with the size of L multiplied by W multiplied by H which is 80 multiplied by 10 multiplied by 4mm according to the GB/T1843 standard, and performing the impact test on 9 impact sample strips of each sample on an impact testing machine.
2. Scratch resistance test
The polypropylene composite material is made into a scraping sample plate, the scraping sample plate is firstly subjected to color difference meter test to measure the absolute value of color shading and darkness difference L1 before scraping, then is subjected to cross scraping by a cross scraping meter according to a cross grid, the scraping test is carried out according to the general standard PV3952, the load is 10N, the diameter of a scraping cone tip is 1mm, the scraping moving speed is 500mm/min, the scraped sample plate is subjected to color difference meter test again to measure the absolute value of color shading and darkness difference L2 after scraping, the values of the two times before and after scraping are subtracted to obtain a determined value, and the value of the color difference Delta L is (L1-L2), and the smaller the value of the color difference Delta L indicates that the scraping resistance.
According to the performance test results of the polypropylene composite material, the mechanical property and the scratch resistance of the polypropylene composite material prepared in the examples 1-4 are better than those of the polypropylene composite material prepared in the comparative examples 1-3. The comparison of examples 1-4 with comparative example 1 shows that the addition of the metal organic framework wollastonite composite particles to the polypropylene plastic improves the scratch resistance and mechanical property of the polypropylene plastic better than the addition of the ordinary wollastonite directly to the polypropylene plastic. Compared with the comparative examples 1 to 4 and 2, the method has the advantage that the scratch resistance and the mechanical property of the polypropylene plastic can be improved by adding the sodium bicarbonate in the preparation process of the metal organic frame wollastonite composite particles. Compared with the comparative example 3, the comparative examples 1 to 4 can obtain that the wollastonite can obviously improve the scratch resistance and the mechanical property of the polypropylene plastic after being pretreated, because a large number of metal organic framework nano particles combined with the surface of the wollastonite fall off from the surface of the wollastonite under the condition of high-temperature melting and pressurization, and the improvement of the wollastonite on the mechanical property of the polypropylene plastic is influenced, the invention utilizes zinc ions and 2-methylimidazole to synthesize metal organic framework nano particles through self-assembly to be deposited and combined in the pits on the surface of the needle-shaped wollastonite, and the electrostatic interaction between carboxyl groups in carboxymethyl chitosan molecules grafted on the surface of the wollastonite and zinc ions on the metal organic framework nano particles forms coordinate bonds, so that the metal organic framework nano particles are stably combined on the surface of the needle-shaped wollastonite, and the polypropylene and the needle-shaped wollastonite are prevented from being melted and blended, the metal organic frame nano particles combined with the surface of the wollastonite fall off from the surface of the wollastonite, so that the scratch resistance and the mechanical property of the wollastonite to polypropylene plastics are improved.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. It will be apparent to those skilled in the art that modifications and variations can be made without departing from the spirit of the invention.
Claims (10)
1. The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material is characterized by comprising the following components in parts by weight:
70-80 parts of polypropylene, 10-20 parts of metal organic framework wollastonite composite particles, 0.2-0.5 part of organic phosphate nucleating agent, 0.1-0.3 part of antioxidant and 0.1-0.3 part of light stabilizer.
2. The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material as claimed in claim 1, wherein the preparation method of the metal organic frame wollastonite composite particles comprises the following steps:
adding zinc nitrate hexahydrate into a methanol solution, stirring and dissolving to obtain a zinc nitrate solution, adding wollastonite and sodium bicarbonate into the zinc nitrate solution, and uniformly dispersing by ultrasonic oscillation to obtain a suspension; adding 2-methylimidazole into a methanol solution, stirring and dissolving to obtain a 2-methylimidazole solution, adding the 2-methylimidazole solution into the suspension, mixing and stirring for 2-5h, carrying out suction filtration, and drying in an oven at 60-70 ℃ for 1-3h to obtain the metal organic framework wollastonite composite particles.
3. The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material as claimed in claim 2, wherein the mass ratio of the wollastonite to the zinc nitrate hexahydrate is 1: 0.3-0.6.
4. The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material as claimed in claim 2, wherein the mixing mass ratio of zinc nitrate hexahydrate and 2-methylimidazole is 1: 5-10.
5. The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material as claimed in claim 2, wherein the wollastonite is pretreated by the following steps:
adding wollastonite into a hydrochloric acid solution for soaking, performing suction filtration and water washing, and then placing the wollastonite in an oven for drying to obtain hydrochloric acid-treated wollastonite; adding an epoxy silane coupling agent into a mixed solution of ethanol and water, uniformly stirring and mixing, adjusting the pH of the system to 3-5, adding wollastonite treated by hydrochloric acid into the mixed solution, heating in a water bath to 50-60 ℃, stirring and reacting for 1-3h, and performing suction filtration, washing and drying to obtain silane coupling agent modified wollastonite; adding carboxymethyl chitosan into deionized water, stirring and dissolving to prepare a carboxymethyl chitosan solution, adding silane coupling agent modified wollastonite into the carboxymethyl chitosan solution, then adding a tin tetrachloride catalyst, heating in a water bath to 70-80 ℃, stirring and reacting for 2-5h, and performing suction filtration, washing and drying to obtain the carboxymethyl chitosan modified wollastonite.
6. The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material as claimed in claim 5, wherein the mass concentration of the hydrochloric acid solution is 0.5-1.0%.
7. The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material as claimed in claim 5, wherein the mixing mass ratio of the wollastonite subjected to hydrochloric acid treatment to the epoxy silane coupling agent is 1: 0.2-0.5.
8. The high-strength scratch-resistant wollastonite modified polypropylene plastic composite material as claimed in claim 5, wherein the mass ratio of the silane coupling agent modified wollastonite to the carboxymethyl chitosan is 1: 0.5-1.
9. A method for preparing the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material as defined in any one of claims 1 to 8, which comprises the following steps:
adding the polypropylene and metal organic frame wollastonite composite particles into a stirrer, stirring for 10-20min at normal temperature, then adding the organic phosphate nucleating agent, the antioxidant and the light stabilizer, continuing stirring for 20-30min to obtain a mixture, adding the mixture into a screw extruder, and performing melt extrusion and granulation to obtain the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material.
10. The preparation method of the high-strength scratch-resistant wollastonite modified polypropylene plastic composite material as claimed in claim 9, wherein the extrusion temperature of the screw extruder is controlled to 180-220 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011082236.6A CN112210166A (en) | 2020-10-12 | 2020-10-12 | High-strength scratch-resistant wollastonite modified polypropylene plastic composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011082236.6A CN112210166A (en) | 2020-10-12 | 2020-10-12 | High-strength scratch-resistant wollastonite modified polypropylene plastic composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112210166A true CN112210166A (en) | 2021-01-12 |
Family
ID=74053238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011082236.6A Withdrawn CN112210166A (en) | 2020-10-12 | 2020-10-12 | High-strength scratch-resistant wollastonite modified polypropylene plastic composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112210166A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011037A (en) * | 2022-06-16 | 2022-09-06 | 太原理工大学 | Polypropylene-based photocatalytic antibacterial master batch and preparation method and application thereof |
-
2020
- 2020-10-12 CN CN202011082236.6A patent/CN112210166A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011037A (en) * | 2022-06-16 | 2022-09-06 | 太原理工大学 | Polypropylene-based photocatalytic antibacterial master batch and preparation method and application thereof |
| CN115011037B (en) * | 2022-06-16 | 2023-09-26 | 太原理工大学 | Polypropylene-based photocatalytic antibacterial master batch and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110951163B (en) | High-surface-tension low-density polypropylene composite material and preparation method thereof | |
| CN113444269A (en) | Low-warpage good-appearance glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN112210166A (en) | High-strength scratch-resistant wollastonite modified polypropylene plastic composite material and preparation method thereof | |
| CN108410093B (en) | High-strength glass fiber modified polyvinyl chloride material and preparation method thereof | |
| CN104845026A (en) | Heat-resistant ABS (acrylonitrile-butadiene-styrene) resin composition high in scratch resistance and preparation method of heat-resistant ABS resin composition | |
| CN112480626B (en) | Glass fiber reinforced polycarbonate composition and preparation method and application thereof | |
| CN111073244B (en) | Polycarbonate composition and preparation method thereof | |
| CN108610559B (en) | Graphene modified polypropylene composite material and preparation method thereof | |
| CN114213792B (en) | PMMA alloy material with high scratch resistance and preparation method thereof | |
| CN106674960B (en) | A kind of electroless coating PC/ABS alloy materials and preparation method thereof suitable for double-shot moulding | |
| CN116144171A (en) | Composite material, preparation method thereof and display device | |
| CN113072779B (en) | Glass fiber reinforced polystyrene composite material and preparation method thereof | |
| CN112123907A (en) | Polytetrafluoroethylene/polypropylene film composite polyvinyl chloride plastic sheet | |
| Aziz et al. | Improving Adhesive Properties of Cellulose Nanocrystals Modifying By 3-Glycidoxypropyltrimethoxy Silane (KH-560) Coupling Agents | |
| CN108485116B (en) | High-strength glass fiber modified polyvinyl chloride material floor and preparation method thereof | |
| CN111607210A (en) | PC flame-retardant composite material for household appliances and preparation method thereof | |
| CN114426732A (en) | Modified long glass fiber reinforced polypropylene composite material and preparation method and application thereof | |
| CN108503978B (en) | High-strength glass fiber modified polyvinyl chloride material building template and preparation method thereof | |
| CN116199975B (en) | Polypropylene modified material and preparation method and application thereof | |
| CN113817318B (en) | Corrosion-resistant, high-temperature-resistant and super-hydrophobic polyphenylene sulfide composite material and preparation method thereof | |
| CN108503980B (en) | High-strength glass fiber modified polyvinyl chloride material door and window profile and preparation method thereof | |
| CN114316444B (en) | Spraying-free long glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN113637261A (en) | Scratch-resistant reinforced PP plastic and preparation method thereof | |
| CN112480634B (en) | Polycarbonate alloy composite material with adjustable surface hardness and preparation method thereof | |
| CN108752834B (en) | High-strength thermoplastic elastomer for charging pile cable and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210112 |
|
| WW01 | Invention patent application withdrawn after publication |