CN112430364A - Special material for regenerated modified PP and PE automotive interior and preparation method thereof - Google Patents
Special material for regenerated modified PP and PE automotive interior and preparation method thereof Download PDFInfo
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention discloses a special material for regenerative modified PP and PE automotive interior trim and a preparation method thereof, wherein the special material comprises the following raw materials in parts by weight: 80-100 parts of recovered particles, 40-45 parts of reinforcing agent, 0.2-0.4 part of isophthalic acid, 4-6 parts of bis-triazine aminostilbene, 1-3 parts of antioxidant and 1-3 parts of light stabilizer; the preparation method comprises the following steps: firstly, adding the recovered particles, the reinforcing agent, the isophthalic acid, the bistriazine aminostilbene, the antioxidant and the light stabilizer into a high-speed mixer, and mixing for 15min to obtain a premix; secondly, pouring the premix into a hot mixer, discharging the mixture to a cold mixer when the hot mixing is carried out to 110 ℃, and then starting the cold mixing to room temperature to obtain dry mixed materials; and melting and blending the dry mixture at 145-155 ℃, and granulating after passing through a double-screw extruder to obtain the special material for the regenerated and modified PP and PE automotive interior trim.
Description
Technical Field
The invention belongs to the technical field of automobile interior trim special materials, and particularly relates to a special material for regenerated and modified PP (polypropylene) and PE (polyethylene) automobile interior trims and a preparation method thereof.
Background
Many automotive interiors are composed of polypropylene (PP) and Polyethylene (PE), also known as plastics. The peculiar smell emitted in normal times is mainly from PP, and the unpleasant smell can be called VOC, namely volatile organic compound. In the industrial production process, propylene is polymerized by a catalyst to become polypropylene, and is required to be transformed into plastic particles by extrusion for the convenience of transportation, and the VOC is generated in granulation. The waste plastic garbage is light and large in volume and stable in chemical property, is difficult to eliminate by the environment after being discarded, can be seen everywhere along with the use of a large amount of plastics, is usually treated by adopting a landfill method, occupies a large amount of land resources due to the landfill of the waste plastic garbage, is stable in property and difficult to degrade, can damage the soil structure after being left in the soil for a long time, causes soil hardening, prevents crops from breathing and absorbing nutrients, and even reduces yield; in addition, a large amount of toxic gas is generated in the incineration treatment, and the atmospheric pollution is caused.
Generally speaking, the current technology and process can not ensure the success rate of polymerization reaction, so that the polymerized substances can move in a volatile manner, and therefore, the unpleasant odor is generated, and the raw materials of the special automobile interior trim materials contain aromatic hydrocarbon and olefin substances, which are main sources of the unpleasant odor of the automobile interior trim.
Disclosure of Invention
The invention provides a special material for regenerative modified PP and PE automotive interior trim and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the raw material of the automobile interior trim special material contains aromatic hydrocarbon and olefin substances, which are main sources of automobile interior trim bad smell, and the burning and landfill treatment of waste plastic wastes pollute the environment.
The purpose of the invention can be realized by the following technical scheme:
the special material for the regenerated modified PP and PE automotive interior comprises the following raw materials in parts by weight:
80-100 parts of recovered particles, 40-45 parts of reinforcing agent, 0.2-0.4 part of isophthalic acid, 4-6 parts of bis-triazine aminostilbene, 1-3 parts of antioxidant and 1-3 parts of light stabilizer;
the special material for the regenerated modified PP and PE automotive interior trim is prepared by the following steps:
firstly, adding the recovered particles, the reinforcing agent, the isophthalic acid, the bistriazine aminostilbene, the antioxidant and the light stabilizer into a high-speed mixer, and mixing for 15min at the rotating speed of 600r/min to obtain a premix;
secondly, pouring the premix into a hot mixer, discharging the mixture to a cold mixer when the hot mixing is carried out to 110 ℃, and then starting the cold mixing to room temperature to obtain dry mixed materials; melting and blending the dry mixture at 145-155 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: cutting at 145 deg.C in the first zone, 165 deg.C in the second zone, 170 deg.C in the third zone, 175 deg.C in the fourth zone, 180 deg.C in the fifth zone, and 175 deg.C in the nose; obtaining the special material for the regenerated modified PP and PE automotive interior.
Further, the recovered particles are prepared by the steps of:
washing the PP and PE reclaimed materials with water, washing for 2 times with ethylene glycol at 35 ℃, drying at the temperature of 100-120 ℃ for 2-4h after washing, crushing into particles with the particle size of 2-4mm, and thus obtaining the reclaimed particles.
Further, the antioxidant is antioxidant 1010; the light stabilizer is light stabilizer 2002.
Further, the enhancer is prepared by the following steps:
step A11, adding graphite powder into a three-neck flask, adding mixed acid at the temperature of 0-5 ℃, slowly adding potassium permanganate, controlling the adding speed of the potassium permanganate to ensure that the temperature of a reaction system is not more than 5 ℃, keeping the temperature unchanged after the potassium permanganate is added, continuously stirring for 30-40min, then raising the temperature to 25 ℃, continuously stirring for 2-4h, after the stirring is finished, adding deionized water with the volume being two times of that of a reaction solution for diluting, raising the temperature to 100 ℃, adding a hydrogen peroxide solution with the mass fraction of 20%, stirring for 6-10min, filtering while hot after the stirring is finished, washing the obtained filter cake for 3 times by using a hydrochloric acid solution with the mass fraction of 3%, washing for 3 times by using the deionized water, and drying at 50 ℃ to constant weight to obtain a carrier a;
step A12, mixing microcrystalline cellulose and absolute ethyl alcohol, setting the temperature to be 48-50 ℃ and the rotating speed to be 400r/min, sequentially adding a sodium hydroxide solution and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, stirring for 4 hours, adjusting the reaction liquid to be neutral, then performing vacuum filtration, mixing the obtained filter cake and ceric ammonium nitrate in equal mass, adding the mixture into deionized water, stirring for 30 minutes at room temperature, then adding 2-acrylamide-2-methylpropanesulfonic acid in equal mass to the filter cake, stirring for 50 minutes at room temperature, then continuing stirring for 3 hours at 40 ℃, performing vacuum filtration, drying the obtained filter cake to constant weight, and obtaining a solid b;
step A13, under the condition of room temperature, mixing a carrier a, a solid b, an auxiliary agent and deionized water according to the mass ratio of 5: 2: 5-10: 15, mixing, and ultrasonically dispersing for 40min under the frequency condition of 60kHz, and freezing for 8h at-70 ℃ to obtain the reinforcing agent.
Further, in the step A11, the mixed acid is sulfuric acid with the mass fraction of 80% and nitric acid with the mass fraction of 78%, and the volume ratio is 9: 1, mixing; the using ratio of the graphite powder, the mixed acid, the potassium permanganate and the hydrogen peroxide solution with the mass fraction of 20% is 1 g: 26-30 mL: 5 g: 150 mL; in the step A12, the concentration of the sodium hydroxide solution is 2-10%; the dosage ratio of the microcrystalline cellulose, the absolute ethyl alcohol, the sodium hydroxide solution and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 1 g: 10-14 mL: 1mL of: 2g of the total weight of the mixture; the volume of the deionized water and the absolute ethyl alcohol are equal.
Further, the auxiliary agent is prepared by the following steps:
step A21, mixing dopamine hydrochloride and deionized water, setting the temperature to be 50 ℃ and the rotating speed to be 200r/min, dropwise adding 1mol/L sodium hydroxide solution, keeping the temperature and the rotating speed unchanged after dropwise adding, continuously stirring for 5 hours, centrifugally washing the obtained reaction liquid for 3-5 times by using the deionized water after stirring, and drying the centrifugally obtained solid to constant weight under the vacuum condition of 40 ℃ to obtain powder c;
and A22, mixing the powder c obtained in the step A21 with an ethanol water solution with the mass fraction of 50%, performing ultrasonic dispersion for 6-10min under the condition that the frequency is 40-50kHz to obtain a dispersion liquid, adding phenyltrimethoxysilane into the dispersion liquid, setting the temperature at 50 ℃ and the rotating speed at 300r/min, stirring for 12-14h, centrifuging the obtained reaction liquid for 16-20min under the condition of 12000r/min after stirring is finished, and drying the centrifuged solid to constant weight under the vacuum condition of 40 ℃ to obtain the assistant.
Further, the dosage ratio of the dopamine hydrochloride, the deionized water and the 1mol/L sodium hydroxide solution in the step A21 is 0.2 g: 100mL of: 0.5-0.7 mL; in the step A22, the dosage ratio of the powder c, the ethanol water solution with the mass fraction of 50 percent and the phenyl trimethoxy silane is 60 mg: 120mL of: 1.3-1.5 g.
Further, the preparation method of the special material for the regenerated and modified PP and PE automotive interior trim comprises the following steps:
firstly, adding the recovered particles, the reinforcing agent, the isophthalic acid, the bistriazine aminostilbene, the antioxidant and the light stabilizer into a high-speed mixer, and mixing for 15min at the rotating speed of 600r/min to obtain a premix;
secondly, pouring the premix into a hot mixer, discharging the mixture to a cold mixer when the hot mixing is carried out to 110 ℃, and then starting the cold mixing to room temperature to obtain dry mixed materials; melting and blending the dry mixture at 145-155 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: cutting at 145 deg.C in the first zone, 165 deg.C in the second zone, 170 deg.C in the third zone, 175 deg.C in the fourth zone, 180 deg.C in the fifth zone, and 175 deg.C in the nose; obtaining the special material for the regenerated modified PP and PE automotive interior.
The invention has the beneficial effects that:
after graphite powder is oxidized by potassium permanganate and hydrogen peroxide, a large number of oxygen-containing functional groups such as hydroxyl, carboxyl and epoxy groups are introduced, conjugated large pi bonds of a carbon plane are damaged by the oxygen-containing functional groups, an sp2 area in the graphite plane is reduced to cause the disorder degree of the graphite plane to be increased, and the random vibration of sp3 carbon atoms is generated to promote the interlayer spacing of the graphite sheet to be increased. 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride as a cationic monomer and 2-acrylamide-2-methylpropanesulfonic acid as an anionic monomer are grafted to the surface of the microcrystalline cellulose, so that the surface with a nano porous structure can be obtained, the porous structure and the surface property of the reinforcing agent can be obtained, the reinforcing agent can be used as a carrier and has a toughening effect, and the recovery efficiency of the PP and PE reclaimed materials is improved.
The method comprises the steps of carrying out surface modification on powder c by using phenyltrimethoxysilane, wherein the powder c is dopamine melanin particles, phenolic hydroxyl groups on the surfaces of the dopamine melanin particles are not completely consumed after the surface modification, a certain free radical scavenging effect is still kept, the heat resistance stability of the prepared special material for the automobile interior trim can be improved by using the modified auxiliary agent, and after the powder c is modified by using the phenyltrimethoxysilane, a phenyl functional group on the phenyltrimethoxysilane can generate stronger interaction with volatile substances such as aromatic substances and olefin substances to generate chemical binding force, so that the desorption is not easy to occur, and the release of the aromatic hydrocarbons and the olefin substances in the special material for the automobile interior trim is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 for the regenerated modified PP and PE automotive interior comprises the following raw materials in parts by weight: 80 parts of recovered particles, 40 parts of reinforcing agent, 0.2 part of isophthalic acid, 46 parts of bis-triazine amino stilbene, 1 part of antioxidant and 1 part of light stabilizer;
the special material for the regenerated modified PP and PE automotive interior trim is prepared by the following steps:
firstly, adding the recovered particles, the reinforcing agent, the isophthalic acid, the bistriazine aminostilbene, the antioxidant and the light stabilizer into a high-speed mixer, and mixing for 15min at the rotating speed of 600r/min to obtain a premix;
secondly, pouring the premix into a hot mixer, discharging to a cold mixer when the temperature of the premix is 100 ℃, and then starting cold mixing to room temperature to obtain dry mixture; melting and blending the dry mixture at 145 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: cutting at 145 deg.C in the first zone, 165 deg.C in the second zone, 170 deg.C in the third zone, 175 deg.C in the fourth zone, 180 deg.C in the fifth zone, and 175 deg.C in the nose; obtaining the special material for the regenerated modified PP and PE automotive interior.
Wherein the recovered particles are prepared by the steps of:
washing the PP and PE reclaimed materials with water, washing for 2 times with ethylene glycol at 35 ℃, drying at 100 ℃ for 2h after washing, crushing into particles with the particle size of 2mm, and thus obtaining the reclaimed particles.
Wherein, the reinforcing agent is prepared by the following steps:
step A11, adding graphite powder into a three-neck flask, adding mixed acid at the temperature of 0 ℃, slowly adding potassium permanganate, controlling the adding speed of the potassium permanganate to ensure that the temperature of a reaction system is not more than 5 ℃, keeping the temperature unchanged after the potassium permanganate is added, continuously stirring for 30min, then raising the temperature to 25 ℃, continuously stirring for 2h, after the stirring is finished, adding deionized water with the volume being twice that of the reaction solution for dilution, raising the temperature to 100 ℃, adding a hydrogen peroxide solution with the mass fraction of 20%, stirring for 60min, filtering while hot after the stirring is finished, washing the obtained filter cake for 3 times by using a hydrochloric acid solution with the mass fraction of 3%, washing for 3 times by using deionized water, and drying at 50 ℃ to constant weight to obtain a carrier a;
step A12, mixing microcrystalline cellulose and absolute ethyl alcohol, setting the temperature to 48 ℃ and the rotating speed to 400r/min, sequentially adding a sodium hydroxide solution and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, stirring for 4 hours, adjusting the reaction liquid to be neutral, then performing vacuum filtration, mixing the obtained filter cake and ceric ammonium nitrate, adding deionized water, stirring for 30 minutes at room temperature, adding 2-acrylamide-2-methylpropanesulfonic acid with the same mass as the filter cake, stirring for 50 minutes at room temperature, then continuing stirring for 3 hours at 40 ℃, performing vacuum filtration, drying the obtained filter cake to constant weight, and obtaining a solid b;
step A13, under the condition of room temperature, mixing a carrier a, a solid b, an auxiliary agent and deionized water according to the mass ratio of 5: 2: 5: 15, mixing, and ultrasonically dispersing for 40min under the frequency condition of 60kHz, and freezing for 8h at-70 ℃ to obtain the reinforcing agent.
Wherein, the mixed acid in the step A11 is sulfuric acid with the mass fraction of 80% and nitric acid with the mass fraction of 78%, and the volume ratio is 9: 1, mixing; the using ratio of the graphite powder, the mixed acid, the potassium permanganate and the hydrogen peroxide solution with the mass fraction of 20% is 1 g: 26mL of: 5 g: 150 mL; the concentration of the sodium hydroxide solution in the step A12 is 2%; the dosage ratio of the microcrystalline cellulose, the absolute ethyl alcohol, the sodium hydroxide solution and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 1 g: 10mL of: 1mL of: 2g of the total weight of the mixture; the volume of the deionized water and the absolute ethyl alcohol are equal.
The auxiliary agent is prepared by the following steps:
step A21, mixing dopamine hydrochloride and deionized water, setting the temperature to be 50 ℃ and the rotating speed to be 200r/min, dropwise adding 1mol/L sodium hydroxide solution, keeping the temperature and the rotating speed unchanged after dropwise adding, continuously stirring for 5 hours, centrifugally washing the obtained reaction liquid for 3 times by using the deionized water after stirring, and drying the centrifugally obtained solid to constant weight under the vacuum condition of 40 ℃ to obtain powder c;
and A22, mixing the powder c obtained in the step A21 with an ethanol water solution with the mass fraction of 50%, performing ultrasonic dispersion for 6min under the condition that the frequency is 40kHz to obtain a dispersion liquid, adding phenyltrimethoxysilane into the dispersion liquid, setting the temperature to be 50 ℃ and the rotating speed to be 300r/min, stirring for 12h, centrifuging the obtained reaction liquid for 16min under the condition of 12000r/min after stirring is finished, and drying the centrifuged solid to constant weight under the vacuum condition of 40 ℃ to obtain the auxiliary agent.
Wherein the dosage ratio of the dopamine hydrochloride, the deionized water and the 1mol/L sodium hydroxide solution in the step A21 is 0.2 g: 100mL of: 0.5 mL; in the step A22, the dosage ratio of the powder c, the ethanol water solution with the mass fraction of 50 percent and the phenyl trimethoxy silane is 60 mg: 120mL of: 1.3 g.
Example 2
The special material for the regenerated modified PP and PE automotive interior comprises the following raw materials in parts by weight: 90 parts of recovered particles, 42 parts of reinforcing agent, 0.3 part of isophthalic acid, 5 parts of bis-triazine amino stilbene, 2 parts of antioxidant and 2 parts of light stabilizer;
the special material for the regenerated modified PP and PE automotive interior trim is prepared by the following steps:
firstly, adding the recovered particles, the reinforcing agent, the isophthalic acid, the bistriazine aminostilbene, the antioxidant and the light stabilizer into a high-speed mixer, and mixing for 15min at the rotating speed of 600r/min to obtain a premix;
secondly, pouring the premix into a hot mixer, discharging to a cold mixer when the temperature of the premix is 105 ℃, and then starting cold mixing to room temperature to obtain dry mixture; melting and blending the dry mixture at 150 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: cutting at 145 deg.C in the first zone, 165 deg.C in the second zone, 170 deg.C in the third zone, 175 deg.C in the fourth zone, 180 deg.C in the fifth zone, and 175 deg.C in the nose; obtaining the special material for the regenerated modified PP and PE automotive interior.
Wherein the recovered particles are prepared by the steps of:
washing the PP and PE reclaimed materials with water, washing for 2 times with ethylene glycol at 35 ℃, drying at 110 ℃ for 3h after washing, crushing into particles with the particle size of 3mm, and thus obtaining the reclaimed particles.
Wherein, the reinforcing agent is prepared by the following steps:
step A11, adding graphite powder into a three-neck flask, adding mixed acid at the temperature of 2 ℃, slowly adding potassium permanganate, controlling the adding speed of the potassium permanganate to ensure that the temperature of a reaction system is not more than 5 ℃, keeping the temperature unchanged after the potassium permanganate is added, continuously stirring for 35min, then raising the temperature to 25 ℃, continuously stirring for 3h, after the stirring is finished, adding deionized water with the volume being twice that of the reaction solution for diluting, raising the temperature to 100 ℃, adding a hydrogen peroxide solution with the mass fraction of 20%, stirring for 8min, filtering while hot after the stirring is finished, washing the obtained filter cake for 3 times by using a hydrochloric acid solution with the mass fraction of 3%, washing for 3 times by using deionized water, and drying at 50 ℃ to constant weight to obtain a carrier a;
step A12, mixing microcrystalline cellulose and absolute ethyl alcohol, setting the temperature to 49 ℃ and the rotating speed to 400r/min, sequentially adding a sodium hydroxide solution and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, stirring for 4 hours, adjusting the reaction liquid to be neutral, then performing vacuum filtration, mixing the obtained filter cake and ceric ammonium nitrate, adding deionized water, stirring for 30 minutes at room temperature, adding 2-acrylamide-2-methylpropanesulfonic acid with the same mass as the filter cake, stirring for 50 minutes at room temperature, then continuing stirring for 3 hours at 40 ℃, performing vacuum filtration, drying the obtained filter cake to constant weight, and obtaining a solid b;
step A13, under the condition of room temperature, mixing a carrier a, a solid b, an auxiliary agent and deionized water according to the mass ratio of 5: 2: 8: 15, mixing, and ultrasonically dispersing for 40min under the frequency condition of 60kHz, and freezing for 8h at-70 ℃ to obtain the reinforcing agent.
Wherein, the mixed acid in the step A11 is sulfuric acid with the mass fraction of 80% and nitric acid with the mass fraction of 78%, and the volume ratio is 9: 1, mixing; the using ratio of the graphite powder, the mixed acid, the potassium permanganate and the hydrogen peroxide solution with the mass fraction of 20% is 1 g: 28mL of: 5 g: 150 mL; the concentration of the sodium hydroxide solution in the step A12 is 8%; the dosage ratio of the microcrystalline cellulose, the absolute ethyl alcohol, the sodium hydroxide solution and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 1 g: 12mL of: 1mL of: 2g of the total weight of the mixture; the volume of the deionized water and the absolute ethyl alcohol are equal.
The auxiliary agent is prepared by the following steps:
step A21, mixing dopamine hydrochloride and deionized water, setting the temperature to be 50 ℃ and the rotating speed to be 200r/min, dropwise adding 1mol/L sodium hydroxide solution, keeping the temperature and the rotating speed unchanged after dropwise adding, continuously stirring for 5 hours, centrifugally washing the obtained reaction solution for 4 times by using the deionized water after stirring, and drying the centrifugally obtained solid to constant weight under the vacuum condition of 40 ℃ to obtain powder c;
and A22, mixing the powder c obtained in the step A21 with an ethanol water solution with the mass fraction of 50%, performing ultrasonic dispersion for 8min under the condition that the frequency is 45kHz to obtain a dispersion liquid, adding phenyltrimethoxysilane into the dispersion liquid, setting the temperature to be 50 ℃ and the rotating speed to be 300r/min, stirring for 12h, centrifuging the obtained reaction liquid for 18min under the condition of 12000r/min after stirring is finished, and drying the centrifuged solid to constant weight under the vacuum condition of 40 ℃ to obtain the auxiliary agent.
Wherein the dosage ratio of the dopamine hydrochloride, the deionized water and the 1mol/L sodium hydroxide solution in the step A21 is 0.2 g: 100mL of: 0.6 mL; in the step A22, the dosage ratio of the powder c, the ethanol water solution with the mass fraction of 50 percent and the phenyl trimethoxy silane is 60 mg: 120mL of: 1.4 g.
Example 3
The special material for the regenerated modified PP and PE automotive interior comprises the following raw materials in parts by weight: 100 parts of recovered particles, 45 parts of reinforcing agent, 0.4 part of isophthalic acid, 6 parts of bis-triazine aminostilbene, 3 parts of antioxidant and 3 parts of light stabilizer;
the special material for the regenerated modified PP and PE automotive interior trim is prepared by the following steps:
firstly, adding the recovered particles, the reinforcing agent, the isophthalic acid, the bistriazine aminostilbene, the antioxidant and the light stabilizer into a high-speed mixer, and mixing for 15min at the rotating speed of 600r/min to obtain a premix;
secondly, pouring the premix into a hot mixer, discharging to a cold mixer when the temperature of the premix is 110 ℃, and then starting cold mixing to room temperature to obtain dry mixture; melting and blending the dry mixture at 155 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: cutting at 145 deg.C in the first zone, 165 deg.C in the second zone, 170 deg.C in the third zone, 175 deg.C in the fourth zone, 180 deg.C in the fifth zone, and 175 deg.C in the nose; obtaining the special material for the regenerated modified PP and PE automotive interior.
Wherein the recovered particles are prepared by the steps of:
washing the PP and PE reclaimed materials with water, washing for 2 times with ethylene glycol at 35 ℃, drying at 120 ℃ for 4h after washing, crushing into particles with the particle size of 4mm, and thus obtaining the reclaimed particles.
Wherein, the reinforcing agent is prepared by the following steps:
step A11, adding graphite powder into a three-neck flask, adding mixed acid at the temperature of 5 ℃, slowly adding potassium permanganate, controlling the adding speed of the potassium permanganate to ensure that the temperature of a reaction system does not exceed 5 ℃, keeping the temperature unchanged after the potassium permanganate is added, continuously stirring for 40min, then raising the temperature to 25 ℃, continuously stirring for 4h, after the stirring is finished, adding deionized water with the volume being twice that of the reaction solution for diluting, raising the temperature to 100 ℃, adding a hydrogen peroxide solution with the mass fraction of 20%, stirring for 10min, filtering while hot after the stirring is finished, washing the obtained filter cake for 3 times by using a hydrochloric acid solution with the mass fraction of 3%, washing for 3 times by using deionized water, and drying at 50 ℃ to constant weight to obtain a carrier a;
step A12, mixing microcrystalline cellulose and absolute ethyl alcohol, setting the temperature to 50 ℃ and the rotating speed to 400r/min, sequentially adding a sodium hydroxide solution and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, stirring for 4 hours, adjusting the reaction liquid to be neutral, then performing vacuum filtration, mixing the obtained filter cake and ceric ammonium nitrate, adding deionized water, stirring for 30 minutes at room temperature, adding 2-acrylamide-2-methylpropanesulfonic acid with the same mass as the filter cake, stirring for 50 minutes at room temperature, then continuing stirring for 3 hours at 40 ℃, performing vacuum filtration, drying the obtained filter cake to constant weight, and obtaining a solid b;
step A13, under the condition of room temperature, mixing a carrier a, a solid b, an auxiliary agent and deionized water according to the mass ratio of 5: 2: 10: 15, mixing, and ultrasonically dispersing for 40min under the frequency condition of 60kHz, and freezing for 8h at-70 ℃ to obtain the reinforcing agent.
Wherein, the mixed acid in the step A11 is sulfuric acid with the mass fraction of 80% and nitric acid with the mass fraction of 78%, and the volume ratio is 9: 1, mixing; the using ratio of the graphite powder, the mixed acid, the potassium permanganate and the hydrogen peroxide solution with the mass fraction of 20% is 1 g: 30mL of: 5 g: 150 mL; in the step A12, the concentration of the sodium hydroxide solution is 2-10%; the dosage ratio of the microcrystalline cellulose, the absolute ethyl alcohol, the sodium hydroxide solution and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 1 g: 14mL of: 1mL of: 2g of the total weight of the mixture; the volume of the deionized water and the absolute ethyl alcohol are equal.
The auxiliary agent is prepared by the following steps:
step A21, mixing dopamine hydrochloride and deionized water, setting the temperature to be 50 ℃ and the rotating speed to be 200r/min, dropwise adding 1mol/L sodium hydroxide solution, keeping the temperature and the rotating speed unchanged after dropwise adding, continuously stirring for 5 hours, centrifugally washing the obtained reaction liquid for 5 times by using the deionized water after stirring, and drying the centrifugally obtained solid to constant weight under the vacuum condition of 40 ℃ to obtain powder c;
and A22, mixing the powder c obtained in the step A21 with an ethanol water solution with the mass fraction of 50%, performing ultrasonic dispersion for 10min under the condition that the frequency is 50kHz to obtain a dispersion liquid, adding phenyltrimethoxysilane into the dispersion liquid, setting the temperature to be 50 ℃ and the rotating speed to be 300r/min, stirring for 14h, centrifuging the obtained reaction liquid for 20min under the condition of 12000r/min after stirring is finished, and drying the centrifuged solid to constant weight under the vacuum condition of 40 ℃ to obtain the auxiliary agent.
Wherein the dosage ratio of the dopamine hydrochloride, the deionized water and the 1mol/L sodium hydroxide solution in the step A21 is 0.2 g: 100mL of: 0.7 mL; in the step A22, the dosage ratio of the powder c, the ethanol water solution with the mass fraction of 50 percent and the phenyl trimethoxy silane is 60 mg: 120mL of: 1.5 g.
Comparative example 1
The comparative example is a common automobile interior trim special material in the market.
The automotive interior exclusive material of examples 1 to 3 and comparative example 1 was subjected to a performance test: testing the volatility of the organic matters of the material, namely taking a sample with certain mass, and standing the sample at 100 ℃ for 10 hours; the volatility of the organic matter of the material is calculated according to a user-defined formula: the% volatility is calculated as (% initial mass of material-mass of material after placement under standard conditions)/initial mass of material × 100%, and a higher value indicates a higher volatility of the organic compound in the material, whereas a lower volatility is obtained. The tensile strength and the elongation at break are tested according to the GB/T1040-2006 standard.
TABLE 1
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Tensile Strength (MPa) | 30.2 | 31.1 | 30.6 | 17.2 |
| Elongation at Break (%) | 172.5 | 171.2 | 171.8 | 120.3 |
| Volatility (%) | 0.12 | 0.13 | 0.12 | 0.8 |
As can be seen from the above table 1, the regenerated modified PP and PE special material for automotive interiors, which is prepared by the invention, releases less aromatic hydrocarbons and olefins and is healthier; meanwhile, the recycled PP and PE materials can also keep better mechanical property, and are more environment-friendly.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The special material for the regenerated modified PP and PE automotive interior is characterized by comprising the following raw materials in parts by weight: 80-100 parts of recovered particles, 40-45 parts of reinforcing agent, 0.2-0.4 part of isophthalic acid, 4-6 parts of bis-triazine aminostilbene, 1-3 parts of antioxidant and 1-3 parts of light stabilizer;
the special material for the regenerated modified PP and PE automotive interior trim is prepared by the following steps:
firstly, adding the recovered particles, the reinforcing agent, the isophthalic acid, the bistriazine aminostilbene, the antioxidant and the light stabilizer into a high-speed mixer, and mixing for 15min at the rotating speed of 600r/min to obtain a premix;
secondly, pouring the premix into a hot mixer, discharging the mixture to a cold mixer when the hot mixing is carried out to 110 ℃, and then starting the cold mixing to room temperature to obtain dry mixed materials; melting and blending the dry mixture at 145-155 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: cutting at 145 deg.C in the first zone, 165 deg.C in the second zone, 170 deg.C in the third zone, 175 deg.C in the fourth zone, 180 deg.C in the fifth zone, and 175 deg.C in the nose; obtaining the special material for the regenerated modified PP and PE automotive interior.
2. The special material for the recycled modified PP and PE automotive interior as claimed in claim 1, wherein the recycled particles are prepared by the following steps:
washing the PP and PE reclaimed materials with water, washing for 2 times with ethylene glycol at 35 ℃, drying at the temperature of 100-120 ℃ for 2-4h after washing, crushing into particles with the particle size of 2-4mm, and thus obtaining the reclaimed particles.
3. The special material for the recycled modified PP and PE automotive interior as claimed in claim 1, wherein the antioxidant is 1010; the light stabilizer is light stabilizer 2002.
4. The special material for the recycled modified PP and PE automotive interior as claimed in claim 1, wherein the reinforcing agent is prepared by the following steps:
step A11, adding graphite powder into a three-neck flask, adding mixed acid at the temperature of 0-5 ℃, slowly adding potassium permanganate, controlling the adding speed of the potassium permanganate to ensure that the temperature of a reaction system is not more than 5 ℃, keeping the temperature unchanged after the potassium permanganate is added, continuously stirring for 30-40min, then raising the temperature to 25 ℃, continuously stirring for 2-4h, after the stirring is finished, adding deionized water with the volume being two times of that of a reaction solution for diluting, raising the temperature to 100 ℃, adding a hydrogen peroxide solution with the mass fraction of 20%, stirring for 6-10min, filtering while hot after the stirring is finished, washing the obtained filter cake for 3 times by using a hydrochloric acid solution with the mass fraction of 3%, washing for 3 times by using the deionized water, and drying at 50 ℃ to constant weight to obtain a carrier a;
step A12, mixing microcrystalline cellulose and absolute ethyl alcohol, setting the temperature to be 48-50 ℃ and the rotating speed to be 400r/min, sequentially adding a sodium hydroxide solution and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, stirring for 4 hours, adjusting the reaction liquid to be neutral, then performing vacuum filtration, mixing the obtained filter cake and ceric ammonium nitrate by mass, adding deionized water, stirring for 30 minutes at room temperature, adding 2-acrylamide-2-methylpropanesulfonic acid by mass equal to that of the filter cake, stirring for 50 minutes at room temperature, then continuing stirring for 3 hours at 40 ℃, performing vacuum filtration, drying the obtained filter cake to constant weight, and obtaining a solid b;
step A13, under the condition of room temperature, mixing a carrier a, a solid b, an auxiliary agent and deionized water according to the mass ratio of 5: 2: 5-10: 15, mixing, and ultrasonically dispersing for 40min under the frequency condition of 60kHz, and freezing for 8h at-70 ℃ to obtain the reinforcing agent.
5. The special material for the regenerated and modified PP and PE automobile interior decoration according to claim 4, wherein the mixed acid in the step A11 is sulfuric acid with a mass fraction of 80% and nitric acid with a mass fraction of 78% in a volume ratio of 9: 1, mixing; the using ratio of the graphite powder, the mixed acid, the potassium permanganate and the hydrogen peroxide solution with the mass fraction of 20% is 1 g: 26-30 mL: 5 g: 150 mL; in the step A12, the concentration of the sodium hydroxide solution is 2-10%; the dosage ratio of the microcrystalline cellulose, the absolute ethyl alcohol, the sodium hydroxide solution and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 1 g: 10-14 mL: 1mL of: 2g of the total weight of the mixture; the volume of the deionized water and the absolute ethyl alcohol are equal.
6. The special material for the recycled modified PP and PE automotive interior as claimed in claim 4, wherein the auxiliary agent is prepared by the following steps:
step A21, mixing dopamine hydrochloride and deionized water, setting the temperature to be 50 ℃ and the rotating speed to be 200r/min, dropwise adding 1mol/L sodium hydroxide solution, keeping the temperature and the rotating speed unchanged after dropwise adding, continuously stirring for 5 hours, centrifugally washing the obtained reaction liquid for 3-5 times by using the deionized water after stirring, and drying the centrifugally obtained solid to constant weight under the vacuum condition of 40 ℃ to obtain powder c;
and A22, mixing the powder c obtained in the step A21 with an ethanol water solution with the mass fraction of 50%, performing ultrasonic dispersion for 6-10min under the condition that the frequency is 40-50kHz to obtain a dispersion liquid, adding phenyltrimethoxysilane into the dispersion liquid, setting the temperature at 50 ℃ and the rotating speed at 300r/min, stirring for 12-14h, centrifuging the obtained reaction liquid for 16-20min under the condition of 12000r/min after stirring is finished, and drying the centrifuged solid to constant weight under the vacuum condition of 40 ℃ to obtain the assistant.
7. The special material for the regenerated and modified PP and PE automobile interior decoration according to claim 6, wherein the dosage ratio of the dopamine hydrochloride, the deionized water and the 1mol/L sodium hydroxide solution in the step A21 is 0.2 g: 100mL of: 0.5-0.7 mL; in the step A22, the dosage ratio of the powder c, the ethanol water solution with the mass fraction of 50 percent and the phenyl trimethoxy silane is 60 mg: 120mL of: 1.3-1.5 g.
8. The preparation method of the special material for the recycled modified PP and PE automotive interior according to claim 1, characterized by comprising the following steps:
firstly, adding the recovered particles, the reinforcing agent, the isophthalic acid, the bistriazine aminostilbene, the antioxidant and the light stabilizer into a high-speed mixer, and mixing for 15min at the rotating speed of 600r/min to obtain a premix;
secondly, pouring the premix into a hot mixer, discharging the mixture to a cold mixer when the hot mixing is carried out to 110 ℃, and then starting the cold mixing to room temperature to obtain dry mixed materials; melting and blending the dry mixture at 145-155 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: cutting at 145 deg.C in the first zone, 165 deg.C in the second zone, 170 deg.C in the third zone, 175 deg.C in the fourth zone, 180 deg.C in the fifth zone, and 175 deg.C in the nose; obtaining the special material for the regenerated modified PP and PE automotive interior.
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