CN112375364A - Special material added with waste mask melt-blown material for automobile exterior trimming parts - Google Patents
Special material added with waste mask melt-blown material for automobile exterior trimming parts Download PDFInfo
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- CN112375364A CN112375364A CN202011337651.1A CN202011337651A CN112375364A CN 112375364 A CN112375364 A CN 112375364A CN 202011337651 A CN202011337651 A CN 202011337651A CN 112375364 A CN112375364 A CN 112375364A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a special material added with a waste mask melt-blown material for automobile exterior trimming parts, which comprises the following raw materials in parts by weight: 80-100 parts of PC resin, 50-60 parts of waste mask reclaimed materials, 10-20 parts of flame-retardant filler, 10-15 parts of modified montmorillonite, 5-10 parts of basalt fiber, 1-5 parts of toughening agent, 1-3 parts of light stabilizer and 1-3 parts of coupling agent; the flame-retardant filler is added to endow the composite material with excellent flame retardant property and heat resistance, the modified montmorillonite and the toughening agent endow the composite material with excellent toughness and impact energy resistance from the aspects of inorganic and organic, the titanium dioxide can scatter ultraviolet rays and absorb ultraviolet rays, the aging resistance of the composite material is improved, secondary efficient utilization of wastes is realized by utilizing a melt-blown material in a waste mask, and pollution is reduced, so that the special material for the automobile exterior trimming part has the characteristics of impact resistance, high temperature resistance, flame retardance, low cost, environmental protection, health and the like.
Description
Technical Field
The invention belongs to the technical field of automobile exterior trim preparation, and particularly relates to a special material for automobile exterior trims, wherein a waste mask melt-blown material is added.
Background
The large-scale epidemic situation which is outbreak in recent years is mainly respiratory infectious diseases, such as COVID-19, SARS, highly pathogenic avian influenza, influenza A H1N1 and the like, the respiratory infectious diseases are spread by droplets and air, and the mask has the characteristics of high spreading speed, wide susceptible population, high morbidity and the like, thereby causing great threat to public health and social stability, being capable of blocking pathogenic microorganisms from invading human bodies when being worn, and being an effective means for preventing the epidemic of the respiratory infectious diseases and protecting the health of personnel.
At present, polypropylene melt-blown non-woven fabric or electret polypropylene melt-blown non-woven fabric is mostly adopted as a filtering barrier layer of a conventional protective mask, most masks are disposable, waste masks are increased, automobile exterior trim is generally formed by injection molding of various engineering plastics, the automobile exterior trim can be illuminated for a long time due to the fact that the automobile exterior trim is arranged outside an automobile, plastics in the prior art are poor in light resistance, after the automobile exterior trim is illuminated, ultraviolet rays cause damage to a plastic molecular structure, mechanical properties are seriously reduced, particularly toughness is obviously reduced, the service life of the automobile exterior trim is seriously influenced, therefore, the waste gas cover melt-blown material is recycled and modified and added into the automobile exterior trim material, and the prepared special automobile exterior trim material which is ageing-resistant and impact-resistant is the technical problem required to be solved by the invention.
Disclosure of Invention
The invention aims to provide a special material for automobile exterior trimming parts, which is added with a waste mask melt-blown material.
The technical problems to be solved by the invention are as follows:
in the prior art, the number of waste masks is large, so that the problems that garbage is increased, resources cannot be reused and the like are caused, and the existing automobile exterior material is poor in impact resistance, flame retardance and aging resistance.
The purpose of the invention can be realized by the following technical scheme:
the special material added with the waste mask melt-blown material for the automobile exterior trimming parts comprises the following raw materials in parts by weight: 80-100 parts of PC resin, 50-60 parts of waste mask reclaimed materials, 10-20 parts of flame-retardant filler, 10-15 parts of modified montmorillonite, 5-10 parts of basalt fiber, 1-5 parts of toughening agent, 1-3 parts of light stabilizer and 1-3 parts of coupling agent;
the preparation method of the special material for the automobile exterior trimming part added with the waste mask melt-blown material comprises the following steps:
adding PC resin and a recovered material of a waste mask into a reaction kettle, heating to 160-200 ℃ at a heating rate of 5 ℃/min, stirring at a rotating speed of 200r/min for 30min, adding a flame-retardant filler, basalt fiber and a coupling agent into the reaction kettle, continuously stirring for 30-50min under the condition of unchanged rotating speed, adding a toughening agent and a light stabilizer, reducing the rotating speed to 100r/min, and stirring for 30min to obtain a mixture;
and secondly, transferring the mixture to an internal mixing extruder for extrusion processing and granulation, wherein the internal mixing speed of an internal mixing part is 50-100r/min, the internal mixing processing temperature is 200-220 ℃, the feeding speed of the extruder is 20-50r/min, the extrusion processing temperature is 200-220 ℃, and the screw rotating speed is 50-200r/min, and finally obtaining the special material for the automobile exterior trimming part added with the waste mask melt-blown material.
Further, the preparation method of the flame-retardant filler comprises the following steps:
step A1, adding ethylene glycol into a three-neck flask, stirring at the rotating speed of 60r/min for 5min under the ice bath condition, dropwise adding phosphorus oxychloride into the three-neck flask while stirring, reacting for 5h, and then dropwise adding a mixed solution a into the three-neck flask at room temperature, wherein the mixed solution a is hexadecanol, tetrahydrofuran and triethylamine according to the dosage ratio of 48.5 g: 20mL of: 1-3g of the mixture, after the dropwise addition, increasing the rotating speed to 200-300r/min, stirring for 20-40min, filtering, removing filter residues, collecting filtrate, adding the filtrate, absolute ethyl alcohol and deionized water into a beaker, heating to a boiling state for reaction for 20min, immediately transferring to an ice bath condition, separating out crystals, washing the crystals for 3-5 times with distilled water, and then drying in a 65 ℃ oven to constant weight to obtain an intermediate 1;
step a2, mixing zinc nitrate hexahydrate and deionized water according to a ratio of 1 g: adding 5-10mL of the intermediate into a flask, adding a sodium hydroxide solution with the mass fraction of 40% into the flask, reacting for 30min at the rotation speed of 80-150r/min, adding a boric acid solution with the mass fraction of 30% into the flask, reacting for 1h at a constant rotation speed, adding the sodium hydroxide solution into the flask to adjust the pH value to 9, adding the intermediate 1 into the flask, stirring for 10min, transferring into a reaction kettle, reacting for 22h at the temperature of 240 ℃ and 245 ℃ at the rotation speed of 200r/min, filtering, washing a filter cake with deionized water until the washing solution is neutral, drying for 10-13h in a 100 ℃ drying oven to obtain an intermediate 2, and adding the intermediate 2 and ammonium polyphosphate according to the mass ratio of 1:1, mixing to obtain the flame-retardant filler.
Further, in the step A1, the dosage ratio of the ethylene glycol, the phosphorus oxychloride and the mixed solution a is 6.2 g: 34 g: 60-70 mL; the volume ratio of the filtrate to the absolute ethyl alcohol to the deionized water is 1:1: 0.5; in the step A2, the dosage ratio of zinc nitrate hexahydrate, deionized water, sodium hydroxide solution with the mass fraction of 40%, boric acid solution with the mass fraction of 30% and the intermediate 1 is 1 g: 5-10 mL: 20mL of: 20mL of: 5g of the total weight.
Further, the preparation method of the modified montmorillonite comprises the following steps:
step S1, mixing hexadecyl tributyl phosphonium bromide, acetone and deionized water according to the weight ratio of 2-3 g: 25mL of: adding 25mL of the mixture into a reaction kettle, magnetically stirring and mixing the mixture for 1h at the room temperature and the controlled rotating speed of 1000r/min to obtain modifier dispersion liquid, and then mixing montmorillonite, ethanol and deionized water according to the weight ratio of 5 g: 50mL of: adding 50mL of the mixture into a three-neck flask, stirring for 0.5h at the temperature of 70 ℃, adding a modifier dispersion liquid into the three-neck flask, stirring for 8h at the temperature of 70 ℃, performing vacuum filtration, alternately washing a filter cake for multiple times by using absolute ethyl alcohol and deionized water until bromide ions cannot be detected by silver nitrate, finally drying for 24h at the temperature of 60 ℃, grinding, and sieving by using a 400-mesh sieve to obtain organic intercalated montmorillonite;
step S2, mixing hexadecyl trimethoxy silane, ethanol and deionized water according to a ratio of 5 mL: 25mL of: adding 25mL of the organic intercalated montmorillonite, ethanol and deionized water into a beaker to adjust the pH value to 4-5, stirring for 1h at room temperature to obtain a silane solution, adding the organic intercalated montmorillonite, ethanol and deionized water obtained in the step S1 into a reaction kettle at the rotation speed of 100-.
Further, in step S1, the dosage ratio of the modifier dispersion liquid to the montmorillonite is 11-13 mL: 1g of a compound; in the step S2, the dosage ratio of the silane solution, the machine-intercalated montmorillonite, the ethanol and the deionized water is 55 mL:5 g: 50mL:50 mL.
Further, the waste mask reclaimed material is obtained by the following steps:
removing a nose bridge strip of the waste mask, making the mask body and the hanging rope of the waste mask into fragments to obtain mask fragments, and drying the mask fragments in an oven at 40-43 ℃ for 3-4h to obtain the recovered material of the waste mask.
Further, the toughening agent is a maleic anhydride grafted styrene-ethylene-butylene-styrene triblock copolymer.
Further, the light stabilizer is titanium dioxide.
Further, the coupling agent is one or a mixture of silane coupling agents KH-151, KH-550, KH-560 and KH-560 according to any proportion.
The invention has the beneficial effects that:
the invention takes PC resin and waste mask reclaimed materials as main materials, and adds flame-retardant filler, modified montmorillonite and other auxiliary agents to prepare a special material for automobile exterior trimming parts added with waste mask melt-blown materials, the addition of the flame-retardant filler endows the composite material with excellent flame-retardant performance and heat resistance, the modified montmorillonite and toughening agent endow the composite material with excellent toughness and impact energy resistance from inorganic and organic aspects, titanium dioxide can scatter ultraviolet rays and absorb ultraviolet rays to improve the anti-aging performance of the composite material, and the melt-blown materials in the waste masks are utilized to realize secondary high-efficiency utilization of wastes and reduce pollution, therefore, the special material for automobile exterior trimming parts has the characteristics of impact resistance, high temperature resistance, flame retardance, low cost, environmental protection, health and the like, in addition, phosphorus oxychloride and ethylene glycol are used as raw materials to prepare an intermediate 1, the intermediate 1 has an anionic surfactant with two hydrophobic groups and two hydrophilic groups, when the flame retardant is reacted with the surface of a zinc borate whisker, the surface of the zinc borate whisker is positively charged, an intermediate 1 is adsorbed on the surface of the zinc borate whisker in the form of an ionic bond, two hydrophilic groups face the surface of the zinc phosphate whisker, two hydrophobic groups face the other side to form an adsorption layer which is arranged in an oriented way, so that the zinc borate whisker presents hydrophobicity and the compatibility of other polymers is improved, the zinc borate is a halogen-free flame retardant and has the advantages of greenness, no toxicity, smoke suppression and high temperature resistance, the flame retardant filler is prepared by compounding the zinc borate and ammonium polyphosphate, the flame retardant filler is added into a polyethylene material, the zinc borate can promote the residue of phosphorus and oxygen in the ammonium polyphosphate while exerting the self flame retardant and smoke suppression characteristics, a more continuous and compact expanded carbon layer can be formed on the surface of carbon to hinder the transfer of heat and the transfer of oxygen, improve the thermal stability of a system and present better flame retardance, the modified montmorillonite is obtained by intercalating hexadecyl tributyl phosphonium bromide into the modified montmorillonite and performing surface treatment on the montmorillonite by using a silane coupling agent on the basis, and the modified montmorillonite can be added into a polyethylene polymer as a stress dispersion point due to the unique lamellar structure of the montmorillonite, so that the toughness and the impact resistance of polymerization are improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The special material added with the waste mask melt-blown material for the automobile exterior trimming parts comprises the following raw materials in parts by weight: 80 parts of PC resin, 50 parts of waste mask reclaimed materials, 10 parts of flame-retardant filler, 10 parts of modified montmorillonite, 5 parts of basalt fiber, 1 part of toughening agent, 1 part of light stabilizer and 1 part of coupling agent;
the preparation method of the special material for the automobile exterior trimming part added with the waste mask melt-blown material comprises the following steps:
adding PC resin and a recovered material of a waste mask into a reaction kettle, heating to 160 ℃ at a heating rate of 5 ℃/min, stirring for 30min at a rotating speed of 200r/min, adding a flame-retardant filler, basalt fiber and a coupling agent into the reaction kettle, continuously stirring for 30min under the condition of unchanged rotating speed, adding a toughening agent and a light stabilizer, reducing the rotating speed to 100r/min, and stirring for 30min to obtain a mixture;
and secondly, transferring the mixture to an internal mixing extruder for extrusion processing and granulation, wherein the internal mixing speed of an internal mixing part is 50r/min, the internal mixing processing temperature is 200 ℃, the feeding speed of the extruder is 20r/min, the extrusion processing temperature is 200 ℃, and the screw rotating speed is 50r/min, and finally obtaining the special material for the automobile exterior trim added with the waste mask melt-blown material.
The preparation method of the flame-retardant filler comprises the following steps:
step A1, adding ethylene glycol into a three-neck flask, stirring at the rotating speed of 60r/min for 5min under the ice bath condition, dropwise adding phosphorus oxychloride into the three-neck flask while stirring, reacting for 5h, and then dropwise adding a mixed solution a into the three-neck flask at room temperature, wherein the mixed solution a is hexadecanol, tetrahydrofuran and triethylamine according to the dosage ratio of 48.5 g: 20mL of: 1g of the mixture is prepared, after the dropwise addition is finished, the rotating speed is increased to 200r/min, the mixture is stirred for 20min, then the mixture is filtered, filter residues are removed, filtrate is collected, the filtrate, absolute ethyl alcohol and deionized water are added into a beaker, the mixture is heated until the boiling reaction is carried out for 20min, the mixture is immediately transferred to an ice bath condition, crystals are separated out, the crystals are washed for 3 times by distilled water and then dried in a 65 ℃ oven to constant weight, and an intermediate 1 is obtained;
step a2, mixing zinc nitrate hexahydrate and deionized water according to a ratio of 1 g: adding 5mL of the intermediate into a flask, adding a sodium hydroxide solution with the mass fraction of 40% into the flask, reacting for 30min at a rotating speed of 80r/min, adding a boric acid solution with the mass fraction of 30% into the flask, reacting for 1h at a constant rotating speed, adding the sodium hydroxide solution into the flask to adjust the pH value to 9, adding the intermediate 1 into the flask, stirring for 10min, transferring into a reaction kettle, reacting for 22h at a temperature of 240 ℃ and a rotating speed of 200r/min, filtering, washing a filter cake with deionized water until the washing liquid is neutral, finally drying for 10h in a 100 ℃ oven to obtain an intermediate 2, and mixing the intermediate 2 and ammonium polyphosphate according to the mass ratio of 1:1, mixing to obtain the flame-retardant filler.
In the step A1, the dosage ratio of the ethylene glycol to the phosphorus oxychloride to the mixed solution a is 6.2 g: 34 g: 60 mL; the volume ratio of the filtrate to the absolute ethyl alcohol to the deionized water is 1:1: 0.5; in the step A2, the dosage ratio of zinc nitrate hexahydrate, deionized water, sodium hydroxide solution with the mass fraction of 40%, boric acid solution with the mass fraction of 30% and the intermediate 1 is 1 g: 5mL of: 20mL of: 20mL of: 5g of the total weight.
The preparation method of the modified montmorillonite comprises the following steps:
step S1, mixing hexadecyl tributyl phosphonium bromide, acetone and deionized water according to the weight ratio of 2 g: 25mL of: adding 25mL of the mixture into a reaction kettle, magnetically stirring and mixing the mixture for 1h at the room temperature and the controlled rotating speed of 1000r/min to obtain modifier dispersion liquid, and then mixing montmorillonite, ethanol and deionized water according to the weight ratio of 5 g: 50mL of: adding 50mL of the mixture into a three-neck flask, stirring for 0.5h at the temperature of 70 ℃, adding a modifier dispersion liquid into the three-neck flask, stirring for 8h at the temperature of 70 ℃, performing vacuum filtration, alternately washing a filter cake for multiple times by using absolute ethyl alcohol and deionized water until bromide ions cannot be detected by silver nitrate, finally drying for 24h at the temperature of 60 ℃, grinding, and sieving by using a 400-mesh sieve to obtain organic intercalated montmorillonite;
step S2, mixing hexadecyl trimethoxy silane, ethanol and deionized water according to a ratio of 5 mL: 25mL of: adding 25mL of the organic intercalated montmorillonite, ethanol and deionized water into a beaker to adjust the pH value to 4, stirring for 1h at room temperature to obtain a silane solution, adding the organic intercalated montmorillonite, the ethanol and the deionized water obtained in the step S1 into a reaction kettle at the rotating speed of 100r/min, stirring for 10min, adding the silane solution into the reaction kettle, heating to 43 ℃, stirring for 24h at the constant rotating speed, carrying out suction filtration, washing a filter cake with the deionized water for 3 times, and drying in an oven at 100 ℃ to constant weight to obtain the modified montmorillonite.
In the step S1, the dosage ratio of the modifier dispersion liquid to the montmorillonite is 11 mL: 1g of a compound; in the step S2, the dosage ratio of the silane solution, the machine-intercalated montmorillonite, the ethanol and the deionized water is 55 mL:5 g: 50mL:50 mL.
The waste mask reclaimed material is obtained by the following steps:
and (3) dismantling a nose bridge strip of the waste mask, making the mask body and the hanging rope of the waste mask into fragments to obtain mask fragments, and drying the mask fragments in an oven at 40 ℃ for 3h to obtain the waste mask reclaimed material.
The toughening agent is a maleic anhydride grafted styrene-ethylene-butylene-styrene triblock copolymer, the light stabilizer is titanium dioxide, and the coupling agent is a silane coupling agent KH-151.
Example 2
The special material added with the waste mask melt-blown material for the automobile exterior trimming parts comprises the following raw materials in parts by weight: 90 parts of PC resin, 55 parts of waste mask reclaimed materials, 15 parts of flame-retardant filler, 12 parts of modified montmorillonite, 8 parts of basalt fiber, 4 parts of toughening agent, 2 parts of light stabilizer and 2 parts of coupling agent;
the preparation method of the special material for the automobile exterior trimming part added with the waste mask melt-blown material comprises the following steps:
adding PC resin and a recovered material of a waste mask into a reaction kettle, heating to 180 ℃ at a heating rate of 5 ℃/min, stirring for 30min at a rotating speed of 200r/min, adding a flame-retardant filler, basalt fiber and a coupling agent into the reaction kettle, continuously stirring for 40min under the condition of unchanged rotating speed, adding a toughening agent and a light stabilizer, reducing the rotating speed to 100r/min, and stirring for 30min to obtain a mixture;
and secondly, transferring the mixture to an internal mixing extruder for extrusion processing and granulation, wherein the internal mixing speed of an internal mixing part is 80r/min, the internal mixing processing temperature is 210 ℃, the feeding speed of the extruder is 30r/min, the extrusion processing temperature is 210 ℃, and the screw rotating speed is 100r/min, and finally obtaining the special material for the automobile exterior trim added with the waste mask melt-blown material.
The preparation method of the flame-retardant filler comprises the following steps:
step A1, adding ethylene glycol into a three-neck flask, stirring at the rotating speed of 60r/min for 5min under the ice bath condition, dropwise adding phosphorus oxychloride into the three-neck flask while stirring, reacting for 5h, and then dropwise adding a mixed solution a into the three-neck flask at room temperature, wherein the mixed solution a is hexadecanol, tetrahydrofuran and triethylamine according to the dosage ratio of 48.5 g: 20mL of: 2g of the mixture is prepared, after the dropwise addition is finished, the rotating speed is increased to 250r/min, the mixture is stirred for 30min, then the mixture is filtered, filter residues are removed, filtrate is collected, the filtrate, absolute ethyl alcohol and deionized water are added into a beaker, the mixture is heated to boiling reaction for 20min, the mixture is immediately transferred to an ice bath condition, crystals are separated out, the crystals are washed for 4 times by distilled water, and then the crystals are dried in a 65 ℃ oven to constant weight, so that an intermediate 1 is obtained;
step a2, mixing zinc nitrate hexahydrate and deionized water according to a ratio of 1 g: adding 8mL of the solution into a flask, adding a sodium hydroxide solution with the mass fraction of 40% into the flask, reacting for 30min at the rotation speed of 120r/min, adding a boric acid solution with the mass fraction of 30% into the flask, reacting for 1h at a constant rotation speed, adding the sodium hydroxide solution into the flask to adjust the pH value to 9, adding the intermediate 1 into the flask, stirring for 10min, transferring into a reaction kettle, reacting for 22h at the temperature of 241 ℃ at the rotation speed of 250r/min, filtering, washing a filter cake with deionized water until the washing liquid is neutral, finally drying for 12h in a 100 ℃ oven to obtain an intermediate 2, and mixing the intermediate 2 and ammonium polyphosphate according to the mass ratio of 1:1, mixing to obtain the flame-retardant filler.
In the step A1, the dosage ratio of the ethylene glycol to the phosphorus oxychloride to the mixed solution a is 6.2 g: 34 g: 65 mL; the volume ratio of the filtrate to the absolute ethyl alcohol to the deionized water is 1:1: 0.5; in the step A2, the dosage ratio of zinc nitrate hexahydrate, deionized water, sodium hydroxide solution with the mass fraction of 40%, boric acid solution with the mass fraction of 30% and the intermediate 1 is 1 g: 8mL of: 20mL of: 20mL of: 5g of the total weight.
The preparation method of the modified montmorillonite comprises the following steps:
step S1, mixing hexadecyl tributyl phosphonium bromide, acetone and deionized water according to the weight ratio of 2 g: 25mL of: adding 25mL of the mixture into a reaction kettle, magnetically stirring and mixing the mixture for 1h at the room temperature and the controlled rotating speed of 1000r/min to obtain modifier dispersion liquid, and then mixing montmorillonite, ethanol and deionized water according to the weight ratio of 5 g: 50mL of: adding 50mL of the mixture into a three-neck flask, stirring for 0.5h at the temperature of 70 ℃, adding a modifier dispersion liquid into the three-neck flask, stirring for 8h at the temperature of 70 ℃, performing vacuum filtration, alternately washing a filter cake for multiple times by using absolute ethyl alcohol and deionized water until bromide ions cannot be detected by silver nitrate, finally drying for 24h at the temperature of 60 ℃, grinding, and sieving by using a 400-mesh sieve to obtain organic intercalated montmorillonite;
step S2, mixing hexadecyl trimethoxy silane, ethanol and deionized water according to a ratio of 5 mL: 25mL of: adding 25mL of the organic intercalated montmorillonite, ethanol and deionized water into a beaker to adjust the pH value to 4, stirring for 1h at room temperature to obtain a silane solution, adding the organic intercalated montmorillonite, ethanol and deionized water obtained in the step S1 into a reaction kettle, stirring for 10min at the rotating speed of 150r/min, adding the silane solution into the reaction kettle, heating to 45 ℃, stirring for 24h at the constant rotating speed, carrying out suction filtration, washing a filter cake with deionized water for 4 times, and drying in an oven at 100 ℃ to constant weight to obtain the modified montmorillonite.
In the step S1, the dosage ratio of the modifier dispersion liquid to the montmorillonite is 12 mL: 1g of a compound; in the step S2, the dosage ratio of the silane solution, the machine-intercalated montmorillonite, the ethanol and the deionized water is 55 mL:5 g: 50mL:50 mL.
The waste mask reclaimed material is obtained by the following steps:
and (3) dismantling a nose bridge strip of the waste mask, making the mask body and the hanging rope of the waste mask into fragments to obtain mask fragments, and drying the mask fragments in a 42 ℃ oven for 3 hours to obtain the waste mask reclaimed material.
The toughening agent is a maleic anhydride grafted styrene-ethylene-butylene-styrene triblock copolymer, the light stabilizer is titanium dioxide, and the coupling agent is a silane coupling agent KH-151.
Example 3
The special material added with the waste mask melt-blown material for the automobile exterior trimming parts comprises the following raw materials in parts by weight: 100 parts of PC resin, 60 parts of waste mask reclaimed materials, 20 parts of flame-retardant filler, 15 parts of modified montmorillonite, 10 parts of basalt fiber, 5 parts of toughening agent, 3 parts of light stabilizer and 3 parts of coupling agent;
the preparation method of the special material for the automobile exterior trimming part added with the waste mask melt-blown material comprises the following steps:
adding PC resin and a recovered material of a waste mask into a reaction kettle, heating to 200 ℃ at a heating rate of 5 ℃/min, stirring for 30min at a rotating speed of 200r/min, adding a flame-retardant filler, basalt fiber and a coupling agent into the reaction kettle, continuously stirring for 50min under the condition of unchanged rotating speed, adding a toughening agent and a light stabilizer, reducing the rotating speed to 100r/min, and stirring for 30min to obtain a mixture;
and secondly, transferring the mixture to an internal mixing extruder for extrusion processing and granulation, wherein the internal mixing speed of an internal mixing part is 100r/min, the internal mixing processing temperature is 220 ℃, the feeding speed of the extruder is 50r/min, the extrusion processing temperature is 220 ℃, and the screw rotating speed is 200r/min, and finally obtaining the special material for the automobile exterior trim added with the waste mask melt-blown material.
The preparation method of the flame-retardant filler comprises the following steps:
step A1, adding ethylene glycol into a three-neck flask, stirring at the rotating speed of 60r/min for 5min under the ice bath condition, dropwise adding phosphorus oxychloride into the three-neck flask while stirring, reacting for 5h, and then dropwise adding a mixed solution a into the three-neck flask at room temperature, wherein the mixed solution a is hexadecanol, tetrahydrofuran and triethylamine according to the dosage ratio of 48.5 g: 20mL of: 3g of the mixture is prepared, after the dropwise addition is finished, the rotating speed is increased to 300r/min, the mixture is stirred for 40min, then the mixture is filtered, filter residues are removed, filtrate is collected, the filtrate, absolute ethyl alcohol and deionized water are added into a beaker, the mixture is heated to boiling reaction for 20min, the mixture is immediately transferred to an ice bath condition, crystals are separated out, the crystals are washed for 5 times by distilled water, and then the crystals are dried in a 65 ℃ oven to constant weight, so that an intermediate 1 is obtained;
step a2, mixing zinc nitrate hexahydrate and deionized water according to a ratio of 1 g: adding 10mL of the intermediate into a flask, adding a sodium hydroxide solution with the mass fraction of 40% into the flask, reacting for 30min at the rotation speed of 150r/min, adding a boric acid solution with the mass fraction of 30% into the flask, reacting for 1h at a constant rotation speed, adding the sodium hydroxide solution into the flask to adjust the pH value to 9, adding the intermediate 1 into the flask, stirring for 10min, transferring into a reaction kettle, reacting for 22h at the temperature of 245 ℃ and the rotation speed of 300r/min, filtering, washing a filter cake with deionized water until the washing liquid is neutral, finally drying for 13h in a 100 ℃ oven to obtain an intermediate 2, and mixing the intermediate 2 and ammonium polyphosphate according to the mass ratio of 1:1, mixing to obtain the flame-retardant filler.
In the step A1, the dosage ratio of the ethylene glycol to the phosphorus oxychloride to the mixed solution a is 6.2 g: 34 g: 70 mL; the volume ratio of the filtrate to the absolute ethyl alcohol to the deionized water is 1:1: 0.5; in the step A2, the dosage ratio of zinc nitrate hexahydrate, deionized water, sodium hydroxide solution with the mass fraction of 40%, boric acid solution with the mass fraction of 30% and the intermediate 1 is 1 g: 10mL of: 20mL of: 20mL of: 5g of the total weight.
The preparation method of the modified montmorillonite comprises the following steps:
step S1, mixing hexadecyl tributyl phosphonium bromide, acetone and deionized water according to the weight ratio of 3 g: 25mL of: adding 25mL of the mixture into a reaction kettle, magnetically stirring and mixing the mixture for 1h at the room temperature and the controlled rotating speed of 1000r/min to obtain modifier dispersion liquid, and then mixing montmorillonite, ethanol and deionized water according to the weight ratio of 5 g: 50mL of: adding 50mL of the mixture into a three-neck flask, stirring for 0.5h at the temperature of 70 ℃, adding a modifier dispersion liquid into the three-neck flask, stirring for 8h at the temperature of 70 ℃, performing vacuum filtration, alternately washing a filter cake for multiple times by using absolute ethyl alcohol and deionized water until bromide ions cannot be detected by silver nitrate, finally drying for 24h at the temperature of 60 ℃, grinding, and sieving by using a 400-mesh sieve to obtain organic intercalated montmorillonite;
step S2, mixing hexadecyl trimethoxy silane, ethanol and deionized water according to a ratio of 5 mL: 25mL of: adding 25mL of the organic intercalated montmorillonite, ethanol and deionized water into a beaker to adjust the pH value to 5, stirring for 1h at room temperature to obtain a silane solution, adding the organic intercalated montmorillonite, the ethanol and the deionized water obtained in the step S1 into a reaction kettle, stirring for 10min at the rotating speed of 200r/min, adding the silane solution into the reaction kettle, heating to 46 ℃, stirring for 24h at the constant rotating speed, carrying out suction filtration, washing a filter cake with the deionized water for 5 times, and drying in an oven at 100 ℃ to constant weight to obtain the modified montmorillonite.
In the step S1, the dosage ratio of the modifier dispersion liquid to the montmorillonite is 13 mL: 1g of a compound; in the step S2, the dosage ratio of the silane solution, the machine-intercalated montmorillonite, the ethanol and the deionized water is 55 mL:5 g: 50mL:50 mL.
The waste mask reclaimed material is obtained by the following steps:
and (3) dismantling a nose bridge strip of the waste mask, making the mask body and the hanging rope of the waste mask into fragments to obtain mask fragments, and drying the mask fragments in an oven at the temperature of 43 ℃ for 4 hours to obtain the waste mask reclaimed material.
The toughening agent is a maleic anhydride grafted styrene-ethylene-butylene-styrene triblock copolymer, the light stabilizer is titanium dioxide, and the coupling agent is a silane coupling agent KH-151.
Comparative example
The local proportion is a common material special for automobile exterior trimming parts in the market.
Examples 1-3 and comparative examples were tested for performance, with the following test criteria: the masterbatches of examples 1 to 3 and comparative example were dried in an oven at 85 ℃ for 4h and then injection molded on an injection molding machine, tensile strength: according to ISO 527-2, tensile speed 50mm/min, flexural strength: according to ISO 178, bending rate of 2mm/min, Vicat softening temperature: according to the ISO 306 standard, condition B50, weather resistance test: irradiation energy of 2500KJ/m according to SAE J2527 method2And 3000KJ/m2The Δ E value of the measured color difference and the PV 3930 method, the test time 1600h, the gradation rating, the test results are shown in the following table:
as can be seen from the above table, in the process of testing the tensile strength, the bending strength and the heat resistance and the aging resistance of the automobile exterior trim, the test results of the examples 1 to 3 are superior to those of the comparative examples, which shows that the special material for the automobile exterior trim prepared by the invention has the performances of heat resistance, flame retardance, impact resistance, aging resistance and the like, and has great application value in the technical field of the preparation of the automobile exterior trim.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. The special material for the automobile exterior trimming part added with the waste mask melt-blown material is characterized by comprising the following raw materials in parts by weight: 80-100 parts of PC resin, 50-60 parts of waste mask reclaimed materials, 10-20 parts of flame-retardant filler, 10-15 parts of modified montmorillonite, 5-10 parts of basalt fiber, 1-5 parts of toughening agent, 1-3 parts of light stabilizer and 1-3 parts of coupling agent;
the preparation method of the special material for the automobile exterior trimming part added with the waste mask melt-blown material comprises the following steps:
adding PC resin and a recovered material of a waste mask into a reaction kettle, heating to 160-200 ℃ at a heating rate of 5 ℃/min, stirring at a rotating speed of 200r/min for 30min, adding a flame-retardant filler, basalt fiber and a coupling agent into the reaction kettle, continuously stirring for 30-50min under the condition of unchanged rotating speed, adding a toughening agent and a light stabilizer, reducing the rotating speed to 100r/min, and stirring for 30min to obtain a mixture;
and secondly, transferring the mixture to an internal mixing extruder for extrusion processing and granulation, wherein the internal mixing speed of an internal mixing part is 50-100r/min, the internal mixing processing temperature is 200-220 ℃, the feeding speed of the extruder is 20-50r/min, the extrusion processing temperature is 200-220 ℃, and the screw rotating speed is 50-200r/min, and finally obtaining the special material for the automobile exterior trimming part added with the waste mask melt-blown material.
2. The material special for the automobile exterior trimming parts added with the melt-blown material of the waste masks as claimed in claim 1, wherein the preparation method of the flame-retardant filler comprises the following steps:
step A1, adding ethylene glycol into a three-neck flask, stirring at the rotating speed of 60r/min for 5min under the ice bath condition, dropwise adding phosphorus oxychloride into the three-neck flask while stirring, reacting for 5h, and then dropwise adding a mixed solution a into the three-neck flask at room temperature, wherein the mixed solution a is hexadecanol, tetrahydrofuran and triethylamine according to the dosage ratio of 48.5 g: 20mL of: 1-3g of the mixture, after the dropwise addition, increasing the rotating speed to 200-300r/min, stirring for 20-40min, filtering, removing filter residues, collecting filtrate, adding the filtrate, absolute ethyl alcohol and deionized water into a beaker, heating to a boiling state for reaction for 20min, immediately transferring to an ice bath condition, separating out crystals, washing the crystals for 3-5 times with distilled water, and then drying in a 65 ℃ oven to constant weight to obtain an intermediate 1;
step a2, mixing zinc nitrate hexahydrate and deionized water according to a ratio of 1 g: adding 5-10mL of the intermediate into a flask, adding a sodium hydroxide solution with the mass fraction of 40% into the flask, reacting for 30min at the rotation speed of 80-150r/min, adding a boric acid solution with the mass fraction of 30% into the flask, reacting for 1h at a constant rotation speed, adding the sodium hydroxide solution into the flask to adjust the pH value to 9, adding the intermediate 1 into the flask, stirring for 10min, transferring into a reaction kettle, reacting for 22h at the temperature of 240 ℃ and 245 ℃ at the rotation speed of 200r/min, filtering, washing a filter cake with deionized water until the washing solution is neutral, drying for 10-13h in a 100 ℃ drying oven to obtain an intermediate 2, and adding the intermediate 2 and ammonium polyphosphate according to the mass ratio of 1:1, mixing to obtain the flame-retardant filler.
3. The special material for the automobile exterior trimming parts, which is added with the melt-blown material of the waste mask, according to claim 2, wherein the dosage ratio of the glycol, the phosphorus oxychloride and the mixed solution a in the step A1 is 6.2 g: 34 g: 60-70 mL; the volume ratio of the filtrate to the absolute ethyl alcohol to the deionized water is 1:1: 0.5; in the step A2, the dosage ratio of zinc nitrate hexahydrate, deionized water, sodium hydroxide solution with the mass fraction of 40%, boric acid solution with the mass fraction of 30% and the intermediate 1 is 1 g: 5-10 mL: 20mL of: 20mL of: 5g of the total weight.
4. The material special for the automobile exterior trimming parts added with the melt-blown material of the waste masks as claimed in claim 1, wherein the preparation method of the modified montmorillonite comprises the following steps:
step S1, mixing hexadecyl tributyl phosphonium bromide, acetone and deionized water according to the weight ratio of 2-3 g: 25mL of: adding 25mL of the mixture into a reaction kettle, magnetically stirring and mixing the mixture for 1h at the room temperature and the controlled rotating speed of 1000r/min to obtain modifier dispersion liquid, and then mixing montmorillonite, ethanol and deionized water according to the weight ratio of 5 g: 50mL of: adding 50mL of the mixture into a three-neck flask, stirring for 0.5h at the temperature of 70 ℃, adding a modifier dispersion liquid into the three-neck flask, stirring for 8h at the temperature of 70 ℃, performing vacuum filtration, alternately washing a filter cake for multiple times by using absolute ethyl alcohol and deionized water until bromide ions cannot be detected by silver nitrate, finally drying for 24h at the temperature of 60 ℃, grinding, and sieving by using a 400-mesh sieve to obtain organic intercalated montmorillonite;
step S2, mixing hexadecyl trimethoxy silane, ethanol and deionized water according to a ratio of 5 mL: 25mL of: adding 25mL of the organic intercalated montmorillonite, ethanol and deionized water into a beaker to adjust the pH value to 4-5, stirring for 1h at room temperature to obtain a silane solution, adding the organic intercalated montmorillonite, ethanol and deionized water obtained in the step S1 into a reaction kettle at the rotation speed of 100-.
5. The material special for the automobile exterior trimming parts added with the melt-blown material of the waste masks as claimed in claim 4, wherein the dosage ratio of the modifier dispersion liquid to the montmorillonite in the step S1 is 11-13 mL: 1g of a compound; in the step S2, the dosage ratio of the silane solution, the machine-intercalated montmorillonite, the ethanol and the deionized water is 55 mL:5 g: 50mL:50 mL.
6. The material special for the automobile exterior trimming parts added with the melt-blown material of the waste mask as claimed in claim 1, wherein the recycled material of the waste mask is obtained by the following steps:
removing a nose bridge strip of the waste mask, making the mask body and the hanging rope of the waste mask into fragments to obtain mask fragments, and drying the mask fragments in an oven at 40-43 ℃ for 3-4h to obtain the recovered material of the waste mask.
7. The material special for the automobile exterior trimming parts added with the melt-blown material of the waste masks as claimed in claim 1, wherein the toughening agent is maleic anhydride grafted styrene-ethylene-butylene-styrene triblock copolymer, the light stabilizer is titanium dioxide, and the coupling agent is one or more of silane coupling agents KH-151, KH-550, KH-560 and KH-560 which are mixed according to any proportion.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115316289A (en) * | 2022-08-10 | 2022-11-11 | 杭州野马医疗器械有限公司 | Dust-free bentonite composite cat litter and preparation method thereof |
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2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115316289A (en) * | 2022-08-10 | 2022-11-11 | 杭州野马医疗器械有限公司 | Dust-free bentonite composite cat litter and preparation method thereof |
| CN115316289B (en) * | 2022-08-10 | 2024-05-07 | 浙江纳巍健康科技有限公司 | Dust-free bentonite composite cat litter and preparation method thereof |
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