CN113462181A - Mould-proof flame-retardant wear-resistant integrated odorless plant fiber reinforced thermoplastic polymer composite material and preparation and application thereof - Google Patents

Mould-proof flame-retardant wear-resistant integrated odorless plant fiber reinforced thermoplastic polymer composite material and preparation and application thereof Download PDF

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CN113462181A
CN113462181A CN202110966033.1A CN202110966033A CN113462181A CN 113462181 A CN113462181 A CN 113462181A CN 202110966033 A CN202110966033 A CN 202110966033A CN 113462181 A CN113462181 A CN 113462181A
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thermoplastic polymer
plant fiber
fiber
modified
composite material
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CN113462181B (en
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程海涛
王翠翠
王戈
顾少华
李明鹏
郑海军
李琪微
李文婷
陈季荷
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International Center for Bamboo and Rattan
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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
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • C08L23/12—Polypropene
    • 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
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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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  • Polymers & Plastics (AREA)
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Abstract

The invention provides a mildew-proof flame-retardant wear-resistant integrated odorless plant fiber reinforced thermoplastic polymer composite material, and a preparation method and application thereof, and belongs to the technical field of automotive interior materials. According to the invention, the interface compatibility of the plant fiber and the thermoplastic polymer is improved by carrying out interface modification treatment on the plant fiber, and the thermoplastic polymer is modified by using the auxiliary agent, so that the composite material has the performances of mould prevention, flame retardance, wear resistance and peculiar smell adsorption, and meanwhile, the interface compatibility with the plant fiber is enhanced.

Description

Mould-proof flame-retardant wear-resistant integrated odorless plant fiber reinforced thermoplastic polymer composite material and preparation and application thereof
Technical Field
The invention relates to the technical field of automotive interior materials, in particular to an odorless plant fiber reinforced thermoplastic polymer composite material integrating mildew resistance, flame retardance and wear resistance, and preparation and application thereof.
Background
With the gradual development of the automobile component industry, the environmental pollution caused by the automobile component industry is increasingly intensified, and the light weight of the automobile is one of the important measures for solving the difficult problem. Researches show that the plant fiber composite material is very suitable for the light weight of automobile parts due to the characteristics of low density, high strength, convenient processing and the like, meets the policy and regulation requirements of 'green environmental protection and low carbonization' in modern society, and is also more and more concerned by automobile host plants.
However, due to the chemical components and the biological structure of the plant fiber raw material, an incompatible interface is generated between the plant fiber and the thermoplastic polymer, which is not beneficial to load transfer, thereby affecting the macroscopic physical and mechanical properties and failing to meet the use requirements of the host factory on the key properties of the polymer-based material.
Disclosure of Invention
The invention aims to provide a mildew-proof flame-retardant wear-resistant integrated odorless plant fiber reinforced thermoplastic polymer composite material, and preparation and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a mildew-proof flame-retardant wear-resistant integrated plant fiber reinforced thermoplastic polymer composite material, which comprises the following steps:
carrying out interface modification on the plant fiber to obtain modified plant fiber;
carrying out blending granulation or self-assembly on the thermoplastic polymer and the auxiliary agent to obtain a modified thermoplastic polymer;
mixing the modified plant fiber and the modified thermoplastic polymer, and spinning to obtain a composite fiber;
sequentially carrying out dust removal, carding and lapping, needle punching to form a felt, hot press molding and edge sealing treatment on the composite fiber to obtain a plant fiber reinforced thermoplastic polymer composite material;
the auxiliary agent comprises an odor adsorbent, a mildew inhibitor, a flame retardant, an anti-wear agent and an interfacial compatilizer.
Preferably, the plant fiber includes one or more of bamboo fiber, hemp fiber, wood fiber, cotton fiber, straw fiber, coconut fiber and banana fiber.
Preferably, the interface modification mode comprises impregnation modification or in-situ modification; the modifier used for the impregnation modification comprises lignin film, KH550, nano calcium carbonate, nano titanium dioxide or polydopamine; the modifiers used for the in-situ modification are calcium chloride and sodium carbonate.
Preferably, the thermoplastic polymer comprises one or more of polyamide, polypropylene, polycarbonate, acrylonitrile-butadiene-styrene, polyethylene terephthalate, polybutylene terephthalate, polyoxymethylene and polylactic acid.
Preferably, the odor adsorbent comprises a physical adsorbent and/or a chemical adsorbent; the physical adsorbent comprises a clay material, porous calcium silicate or zeolite; the chemical adsorbent comprises rosin ester, zinc ricinoleate, vinyl POSS modified nanoparticles or methyl propenyl POSS modified nanoparticles.
Preferably, the mildew preventive comprises a main mildew preventive and a synergistic mildew preventive; the main mildew preventive comprises chitosan, cassia oil, allicin, camphor powder or zinc borate; the synergistic mildew preventive comprises zinc oxide, cuprous oxide, nano silver, nano titanium dioxide, quaternary ammonium salt or o-phenylphenol; the content ratio of the main mildew preventive and the synergistic mildew preventive in the thermoplastic polymer is (1-5) wt% to (0-3) wt%; the interfacial compatilizer is maleic anhydride grafted compatilizer, and the interfacial compatilizer comprises maleic anhydride grafted polyolefin, maleic anhydride grafted POE or maleic anhydride grafted SEBS.
Preferably, the mass percentages of the odor adsorbent, the mildew preventive, the flame retardant, the wear-resistant agent and the interfacial compatilizer in the thermoplastic polymer are 1-10 wt%, 1-8 wt%, 5-30 wt%, 1-20 wt% and 1-5 wt% in sequence; and the mass contents of the modified plant fiber and the thermoplastic polymer are 25-65 wt% and 35-75 wt% in sequence, wherein the total mass content of the modified plant fiber and the thermoplastic polymer is 100%.
Preferably, the hot-press forming temperature is 180-230 ℃, the pressure is 0.5-5.0 MPa, and the time is 2-20 min.
The invention provides the plant fiber reinforced thermoplastic polymer composite material prepared by the preparation method in the technical scheme.
The invention provides an application of the plant fiber reinforced thermoplastic polymer composite material in an automotive interior material.
The invention provides a preparation method of a mildew-proof flame-retardant wear-resistant integrated plant fiber reinforced thermoplastic polymer composite material, which comprises the following steps: carrying out interface modification on the plant fiber to obtain modified plant fiber; carrying out blending granulation or self-assembly on the thermoplastic polymer and the auxiliary agent to obtain a modified thermoplastic polymer; mixing the modified plant fiber and the modified thermoplastic polymer, and spinning to obtain a composite fiber; sequentially carrying out dust removal, carding and lapping, needle punching to form a felt, hot press molding and edge sealing treatment on the composite fiber to obtain a plant fiber reinforced thermoplastic polymer composite material; the auxiliary agent comprises an odor adsorbent, a mildew inhibitor, a flame retardant, an anti-wear agent and an interfacial compatilizer. According to the invention, the interface compatibility of the plant fiber and the thermoplastic polymer is improved by carrying out interface modification treatment on the plant fiber, and the interface modification can enable the internal conduit and the thin-walled tissue of the plant fiber to be wrapped by the thermoplastic polymer to form a closed pore structure, reduce the moisture adsorption sites on the surface of the fiber, reduce the sites contacted with mould, reduce the stress concentration damage of the material, and improve the dimensional stability of the material, so that the mould-proof, flame-retardant and wear-resistant properties of the material are improved; meanwhile, the thermoplastic polymer is modified by using the auxiliary agent, so that the composite material has the characteristics of mildew resistance, flame retardance, wear resistance and no odor, and the interface compatibility with the plant fiber is enhanced.
The plant fiber reinforced thermoplastic polymer composite material prepared by the invention has the advantages of no odor, environmental protection, light weight, low modulus, high strength, uniform structure, water resistance, mildew resistance, flame retardance and wear resistance, and has the characteristic of integration of mildew resistance, flame retardance, wear resistance and no odor, so that the plant fiber reinforced thermoplastic polymer composite material can be used for automotive interior trims such as inner lining doors, ceilings, luggage racks and the like.
The preparation method has simple process, the used raw materials are cheap and easy to obtain, and the method has the advantages of cost reduction and efficiency improvement.
Detailed Description
The invention provides a preparation method of a mildew-proof flame-retardant wear-resistant integrated plant fiber reinforced thermoplastic polymer composite material, which comprises the following steps:
carrying out interface modification on the plant fiber to obtain modified plant fiber;
carrying out blending granulation or self-assembly on the thermoplastic polymer and the auxiliary agent to obtain a modified thermoplastic polymer;
mixing the modified plant fiber and the modified thermoplastic polymer, and spinning to obtain a composite fiber;
sequentially carrying out dust removal, carding and lapping, needle punching to form a felt, hot press molding and edge sealing treatment on the composite fiber to obtain a plant fiber reinforced thermoplastic polymer composite material;
the auxiliary agent comprises an odor adsorbent, a mildew inhibitor, a flame retardant, an anti-wear agent and an interfacial compatilizer.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention carries out interface modification on the plant fiber to obtain the modified plant fiber. In the present invention, the plant fiber preferably includes one or more of bamboo fiber, hemp fiber, wood fiber, cotton fiber, straw fiber, coconut fiber and banana fiber; when the plant fibers are a plurality of the plant fibers, the mixture ratio of different kinds of plant fibers is not specially limited, and the plant fibers can be mixed at any ratio.
In the present invention, the interfacial modification preferably includes impregnation modification or in-situ modification; the modifying agent used for the impregnation modification preferably comprises KH550, nano calcium carbonate, nano titanium dioxide or polydopamine; the impregnation modification is preferably carried out under atmospheric pressure or vacuum conditions.
In the invention, when the modifier is nano calcium carbonate or nano titanium dioxide, the process of the impregnation modification preferably comprises the steps of putting the plant fiber into deionized water, stirring for 30min, then adding the dispersant and the modifier, continuing stirring for 25min, washing the obtained suspension with the deionized water under a 200-mesh nylon net until no obvious particles exist, and drying in an oven at room temperature or 103 +/-2 ℃ to obtain the modified plant fiber. In the invention, the dispersant is preferably EDTA-2Na, and the mass ratio of the plant fiber, the dispersant and the modifier is preferably 100:1.7: 20.
When the modifier is polydopamine, the dipping modification process is preferably to put the plant fiber into deionized water, stir for 30min, add the dopamine, continue stirring for 24h, perform oxidative self-polymerization deposition on the surface of the plant fiber by taking oxygen in the air as an oxidant under the normal pressure condition, wash the obtained suspension to be colorless with the deionized water under a 200-mesh nylon net, and dry the suspension in an oven at room temperature or 103 +/-2 ℃ to obtain the modified plant fiber. In the present invention, the mass ratio of the plant fiber to the polydopamine is preferably 100: 0.67. Alternatively, the oxidative autodeposition is preferably carried out under vacuum conditions, the oxidizing agent used is preferably sodium periodate, and the molar ratio of the oxidizing agent to the polydopamine is preferably 1: 1.
When the modifier is KH550, the soaking modification process is preferably to add KH550 into absolute ethyl alcohol, stir for 5min, add plant fibers into the obtained mixed solution, continue stirring for 25min, seal and stand for 30min by using a preservative film (fully grafting KH550 and the plant fibers), wash the obtained product with deionized water, and dry the product in an oven at room temperature or 103 +/-2 ℃ to obtain the modified plant fibers. In the invention, the mass ratio of the KH550 to the absolute ethyl alcohol is preferably 1: 49; the mass ratio of the plant fiber to the mixed solution is preferably 1: 20.
The other steps in the impregnation modification process are not particularly limited in the present invention, and may be performed according to a process well known in the art.
The invention adopts dipping modification, so that longitudinal grooves, veins and cavities on the surface of the fiber provide force points for loading nano calcium carbonate or nano titanium dioxide or polydopamine or KH550 to form a rivet lock structure, thereby improving the interface combination of the plant fiber and the polymer.
In the present invention, the modifying agent used for the in situ modification is preferably calcium chloride and sodium carbonate; the in-situ modification process is preferably carried out by mixing plant fibers with CaCl at room temperature2Mixing the solution at 60r/min for 30min, draining with 20 mesh sieve, and adding Na2CO3Stirring the solution for 25min, filtering with 20 mesh sieve, washing the obtained filtrate with pure water, standing at room temperature or 103 + -2 deg.C in oven until there are no obvious inorganic particlesDrying to obtain the modified plant fiber. In the present invention, the CaCl is2Solution and Na2CO3The molar concentration ratio of the solution is preferably 1:1 or 1:2 or 2: 1. The dosage ratio of the plant fiber to the calcium chloride and the sodium carbonate is not specially limited, and CaCO can be formed on the surface of the plant fiber in situ by using excessive calcium chloride saturated solution and sodium carbonate saturated solution3And (4) granulating.
The invention adopts an ion reaction method to synthesize CaCO in situ3Particles, in supersaturated solution, Ca2+And CO3 2-Precipitation reaction to form CaCO3Molecular clusters due to CaCO3The molecular clusters have high solubility and large specific surface energy, so in order to reduce Gibbs free energy of the system, the molecular clusters begin to aggregate to form crystal nuclei and stably grow into crystal particles; CaCO3The particles are mainly deposited in grooves and 'cavities' on the surface of the plant fiber to form a rivet lock catch structure, so that the interface compatibility of the plant fiber and the thermoplastic polymer is improved, the size stability of the composite material is improved, and simultaneously, the calcium carbonate can be used as a flame retardant, so that a calcium carbonate flame-retardant layer is constructed on the surface of the plant fiber, and the flame retardant property of the composite material is improved.
After the interface modification is finished, the modified plant fiber is preferably subjected to heat treatment, hydrothermal treatment or microwave treatment to obtain the modified plant fiber; the invention removes the smell of the plant fiber through heat treatment, hydrothermal treatment or microwave treatment and enables the fiber to be physically mildewproof. In the invention, the heat treatment process is preferably drying treatment at 130-190 ℃ by using an oven; the drying time is not particularly limited in the present invention, and may be performed according to a process known in the art.
In the invention, the hydrothermal treatment process is preferably carried out by boiling in water for 1-5 h in a water bath kettle at 60-100 ℃ and then drying. In the invention, the microwave treatment process preferably adopts ultrapure water to soak the modified plant fiber for 5-24 h, and then carries out microwave heating treatment; the microwave heating treatment time is not specially limited, and the materials can be dried.
According to the invention, the plant fiber is subjected to interface modification, so that the inner conduit and the thin-walled tissue of the fiber are wrapped by the thermoplastic polymer to form a closed pore structure, the moisture adsorption sites on the surface of the fiber are reduced, the sites in contact with mould are reduced, the stress concentration damage of the material is reduced, and the stability of the material is improved, thereby improving the mould-proof, flame-retardant and wear-resistant properties of the material. Therefore, the surface of the plant fiber is subjected to interface modification, so that the mildew-proof, flame-retardant and wear-resistant effects can be synergistically exerted.
The invention carries out blending granulation or self-assembly on the thermoplastic polymer and the auxiliary agent to obtain the modified thermoplastic polymer. In the present invention, the thermoplastic polymer preferably includes one or more of Polyamide (PA), polypropylene (PP), Polycarbonate (PC), Acrylonitrile Butadiene Styrene (ABS), Polyethylene (PE), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyoxymethylene (POM), and polylactic acid (PLA); when the thermoplastic polymer is preferably selected from the above-mentioned thermoplastic polymers, the ratio of the thermoplastic polymers of different types is not particularly limited, and any ratio may be used.
In the present invention, the auxiliary agents include odor adsorbents, mold inhibitors, flame retardants, wear-resistant agents, and interfacial compatibilizers.
In the present invention, the odor adsorbent preferably comprises a physical adsorbent and/or a chemical adsorbent; the physical adsorbent preferably comprises a clay material, porous calcium silicate or zeolite; the clay material preferably comprises organic bentonite, nano montmorillonite, diatomite, attapulgite or halloysite. In the present invention, the chemisorbent preferably comprises rosin ester, zinc ricinoleate, vinyl POSS modified nanoparticles or methacryl POSS modified nanoparticles. The sources of the vinyl POSS modified nanoparticles and the methacrylic POSS modified nanoparticles are not particularly limited in the present invention, and commercially available products well known in the art may be used. The odor adsorbent is used for isolating or adsorbing odor source molecules in the preparation process of the composite material, and the content of the odor source molecules is lower than a detection threshold value.
In the present invention, the mildewcide preferably includes a main mildewcide and a synergistic mildewcide; the main mildew preventive preferably comprises chitosan, cassia oil, allicin, camphor powder or zinc borate; the synergistic mildew preventive preferably comprises zinc oxide, cuprous oxide, nano silver, nano titanium dioxide, quaternary ammonium salt or o-phenylphenol; the quaternary ammonium salt is preferably organosilicon quaternary ammonium salt or organosilicon quaternary ammonium salt mildew preventive; the sources of the organosilicon quaternary ammonium salt and the organosilicon quaternary ammonium salt mildew preventive are not particularly limited, and the organosilicon quaternary ammonium salt mildew preventive is commercially available and well known in the field. In the invention, the content ratio of the main mildew inhibitor and the synergistic mildew inhibitor in the thermoplastic polymer is preferably (1-5) wt% to (0-3) wt%, more preferably (2-3) wt% to (1-2) wt%. The invention utilizes the mildew inhibitor to inhibit the growth of the mildew, realizes the mildew-proof effect, reduces the cost and improves the efficiency.
In the present invention, the flame retardant preferably includes one or more of an intumescent flame retardant and an inorganic flame retardant; the intumescent flame retardant preferably comprises beta-cyclodextrin, starch, cellulose, chitosan, expandable graphite, ammonium polyphosphate, melamine polyphosphate or pentaerythritol; the inorganic flame retardant preferably comprises aluminum hydroxide, magnesium hydroxide or antimony trioxide; the flame retardant preferably further comprises basic magnesium sulfate whisker synergistic microcapsule red phosphorus, lauric acid, capric acid, myristic acid, paraffin and/or aluminum hypophosphite. When the flame retardant is preferably selected from the above flame retardants, the invention has no special limitation on the mixture ratio of different flame retardants, and the mixture ratio can be any. According to the invention, a tight flame-retardant layer is formed on the surface of the composite material by adding the flame retardant, so that the exchange and energy conduction of substances inside and outside the composite material are isolated or reduced.
In the invention, the wear-resisting agent preferably comprises one or more of floating beads, hollow microspheres, talcum powder, silicon micropowder and nano ceramic, and the hollow microspheres preferably comprise hollow glass microspheres, hollow ceramic microspheres or hollow floating beads; the nano ceramic is preferably nano silicon nitride, nano titanium nitride, nano silicon carbide, nano titanium carbide or nano zirconium carbide. The invention utilizes the wear-resisting agent to improve the wear resistance of the composite material.
In the present invention, the interfacial compatibilizer is preferably a maleic anhydride grafted compatibilizer, and the interfacial compatibilizer preferably includes maleic anhydride grafted polyolefin, maleic anhydride grafted POE, or maleic anhydride grafted SEBS.
In the invention, the mass percentages of the odor adsorbent, the mildew preventive, the flame retardant, the wear-resistant agent and the interfacial compatilizer in the thermoplastic polymer are preferably 1-10 wt%, 1-8 wt%, 5-30 wt%, 1-20 wt% and 1-5 wt% in sequence, and more independently are preferably 3-8 wt%, 2-6 wt%, 10-20 wt%, 5-15 wt% and 2-3 wt% in sequence.
In the invention, the blending and granulating process is preferably to blend the thermoplastic polymer and the auxiliary agent in a high-speed mixer for 25-45 min, then to granulate in a granulator, and to granulate the obtained material in a granulator to obtain the modified thermoplastic polymer. The invention has no special limitation on the rotation speed of the blending and can ensure that the materials are fully and uniformly mixed. In the present invention, the temperatures of the first zone to the fourth zone of the pelletizer are preferably 150. + -. 10 ℃, 170. + -. 10 ℃, 190. + -. 10 ℃ and 160. + -. 10 ℃ in this order. The present invention does not specifically limit the pelletizer, the pelletizing and the granulating processes and the particle size of the obtained material, and the processes well known in the art can be performed.
In the invention, the self-assembly process is preferably to carry out layer-by-layer self-assembly on the thermoplastic polymer and the auxiliary agent under the driving of the shearing force, and the specific process is preferably to place the thermoplastic polymer and the auxiliary agent in two extruders respectively, and sequentially carry out extrusion through a co-extrusion die head, a lamination-multiplication element, a die opening, cooling and shaping, and granulation through a granulator to obtain the modified thermoplastic polymer. The specific processes of extrusion through a co-extrusion die, a lamination-multiplication element, a die, cooling and shaping and granulating by a granulator are not particularly limited in the invention, and the processes well known in the art can be carried out. The invention utilizes the co-extrusion die head and the lamination-multiplication element to adjust and control the dispersion and distribution condition of the auxiliary agent, so that the modified thermoplastic polymer has the functions of mildew resistance, flame retardance and wear resistance.
After the modified plant fiber and the modified thermoplastic polymer are obtained, the modified plant fiber and the modified thermoplastic polymer are mixed and spun to obtain the composite fiber. In the invention, the mass content of the modified plant fiber and the thermoplastic polymer is preferably 25 to 65 wt% and 35 to 75 wt%, more preferably 30 to 50 wt% and 50 to 70 wt% in this order, based on 100% of the total mass content of the modified plant fiber and the thermoplastic polymer. The spinning parameters are not particularly limited in the present invention, and the melt viscosity and temperature can be determined according to the molecular weight of the thermoplastic polymer used according to procedures well known in the art.
After the composite fiber is obtained, the composite fiber is subjected to dust removal, carding and lapping, needle punching to form a felt, hot press forming and edge sealing treatment in sequence to obtain the plant fiber reinforced thermoplastic polymer composite material. In the present invention, the carding and lapping mode is preferably mechanical carding and lapping or airflow carding and lapping. The manner in which the dust is removed, carded and lapped, and needle punched into a mat is not particularly limited in the present invention and may be performed according to procedures well known in the art. In the invention, the hot-press forming temperature is preferably 180-230 ℃, more preferably 190-220 ℃, the pressure is preferably 0.5-5.0 MPa, more preferably 1.0-4.0 MPa, and the time is preferably 2-20 min, more preferably 5-15 min.
In the invention, the edge sealing treatment is preferably performed by using an organic polymer film or a nano cellulose film; the organic polymer film is preferably a polypropylene film. The source and specification of the organic polymer film or the nano cellulose film are not particularly limited in the present invention, and commercially available products well known in the art may be used. The invention has no special limit on the process and material consumption of the edge sealing treatment, and can completely seal the edge. The invention ensures that the composite material absorbs formaldehyde and reduces odor through edge sealing treatment.
The invention provides the plant fiber reinforced thermoplastic polymer composite material prepared by the preparation method in the technical scheme.
The invention provides an application of the plant fiber reinforced thermoplastic polymer composite material in an automotive interior material. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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
Adding 40g of KH550 into 1960g of absolute ethanol, stirring for 5min, then adding 100g of bamboo fiber, continuing stirring for 25min, sealing and standing for 30min by using a preservative film, washing and drying the obtained product by using deionized water, and then placing the product into a drying oven at 150 ℃ for heat treatment to obtain modified bamboo fiber;
mixing polypropylene and an auxiliary agent (5 wt% of porous calcium silicate, 3 wt% of cassia oil, 1.5 wt% of nano titanium dioxide, 15 wt% of basic magnesium sulfate whisker and microcapsule red phosphorus, 10 wt% of hollow glass beads and 2.5 wt% of maleic anhydride grafted polypropylene) in a high-speed mixer for 30min, then placing the mixture in a granulator for granulation, and granulating the obtained material in a granulator to obtain modified polypropylene, wherein the temperatures of a first area to a fourth area of the granulator are 150 +/-10 ℃, 170 +/-10 ℃, 190 +/-10 ℃ and 160 +/-10 ℃ in sequence;
and (2) carrying out mixed spinning on the modified bamboo fiber and the modified polypropylene according to the proportion of 50 wt% to 50 wt%, sequentially carrying out dust removal, mechanical carding and lapping and needle punching on the obtained composite fiber to form a felt, carrying out hot press molding (the temperature is 190 ℃, the pressure is 0.6MPa, and the time is 5min), and carrying out edge sealing treatment on the obtained molded body by adopting a polypropylene film to obtain the bamboo fiber reinforced polypropylene composite material.
Example 2
According to the raw material proportion and the steps of the embodiment 1, KH550 is respectively adopted to carry out interface modification on bamboo fibers and hemp fibers, and 35 wt% of the obtained modified bamboo fibers and 15 wt% of the obtained modified hemp fibers are put into an oven at 170 ℃ for heat treatment to obtain modified compound fibers;
mixing polypropylene and an auxiliary agent (5 wt% of nano montmorillonite, 3 wt% of chitosan and 1.5 wt% of nano titanium dioxide, 15 wt% of expandable graphite, 10 wt% of floating beads and 2.5 wt% of maleic anhydride grafted poly-POE) in a high-speed mixer for 30min, then placing the mixture in a granulator for granulation, and granulating the obtained material in a granulator, wherein the temperatures of a first zone to a fourth zone of the granulator are 150 +/-10 ℃, 170 +/-10 ℃, 190 +/-10 ℃ and 160 +/-10 ℃ in sequence to obtain modified polypropylene;
and (2) carrying out mixed spinning on the modified compound fiber and the modified polypropylene according to the proportion of 50 wt% to 50 wt%, sequentially carrying out dust removal, mechanical carding and lapping and needle punching on the obtained composite fiber to form a felt, carrying out hot press molding (the temperature is 190 ℃, the pressure is 0.8MPa, and the time is 5min), and carrying out edge sealing treatment on the obtained molded body by adopting a nano cellulose membrane to obtain the bamboo fiber reinforced polypropylene composite material.
Example 3
According to the raw material proportion and the steps of the embodiment 1, KH550 is respectively adopted to respectively carry out interface modification on bamboo fibers and wood fibers, and 35 wt% of the obtained modified bamboo fibers and 15 wt% of the obtained modified wood fibers are put into an oven at 190 ℃ for heat treatment to obtain modified compound fibers;
blending polypropylene and an auxiliary agent (halloysite 5 wt%, camphor powder 3 wt% + nano titanium dioxide 1.5 wt%, lauric acid 15 wt%, talcum powder 10 wt%, maleic anhydride grafted polypropylene 2.5 wt%) in a high-speed mixer for 30min, then placing the mixture in a granulator for granulation, and granulating the obtained material in a granulator, wherein the temperatures of a first area to a fourth area of the granulator are 150 +/-10 ℃, 170 +/-10 ℃, 190 +/-10 ℃ and 160 +/-10 ℃ in sequence to obtain modified polypropylene;
and (2) carrying out mixed spinning on the modified compound fiber and the modified polypropylene according to the proportion of 50 wt% to 50 wt%, sequentially carrying out dust removal, mechanical carding and lapping and needle punching on the obtained composite fiber to form a felt, carrying out hot press molding (the temperature is 190 ℃, the pressure is 0.7MPa, and the time is 5min), and carrying out edge sealing treatment on the obtained molded body by adopting a nano cellulose membrane to obtain the bamboo fiber reinforced polypropylene composite material.
Comparative example 1
Drying 50 wt% of bamboo fiber at 150 ℃, compounding the bamboo fiber with 50 wt% of polypropylene to form a felt, and carrying out hot press molding for 5min under the conditions of 190 ℃ and 0.6MPa of pressure to obtain the composite material.
Performance testing
The composite materials prepared in examples 1-3 and comparative example 1 were subjected to performance tests, and the national standards or methods used for each test item were as follows:
unit square gram weight: weighing the mass of each sample by a balance, dividing the mass by the area, and calculating an average value; density: GB/T1.33.1-2008; flexural strength and flexural modulus ASTM D790-10; a limiting oxygen index ASTM D2863-19; coefficient of thermal conductivity: ASTM D5470; mold control efficacy: GB/T18261-2013; water absorption: GB/T1034-2008; surface abrasion resistance GB/T15102-2006;
odor grade: before the test, the sample is placed for 24 hours under the conditions that the temperature is 23 +/-2 ℃ and the relative humidity is 50% +/-10%, the sample is placed into a sealed glass container, the container is placed in a constant temperature and humidity box at 40 ℃ or 80 ℃ for 2 hours, and the container is taken out for evaluation.
TABLE 1 Performance data for composites prepared in examples 1-3 and comparative example 1
Figure BDA0003223959340000101
Figure BDA0003223959340000111
As can be seen from table 1, the composite material prepared by the present invention has high flexural modulus, flexural strength and limiting oxygen index, and is excellent in surface abrasion resistance and water absorption rate, which indicates that the composite material prepared by the present invention has excellent interfacial compatibility between the fibers and the thermoplastic polymer. The raw materials used in the invention have low density and environmental protection, so the obtained composite material has low density and light weight. Moreover, the dimensional change rate of the material is small, which indicates that the structure of the composite material is uniform; and the prepared composite material has excellent flame retardance, corrosion resistance, mildew resistance and water resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the mould-proof flame-retardant wear-resistant integrated odorless plant fiber reinforced thermoplastic polymer composite material is characterized by comprising the following steps of:
carrying out interface modification on the plant fiber to obtain modified plant fiber;
carrying out blending granulation or self-assembly on the thermoplastic polymer and the auxiliary agent to obtain a modified thermoplastic polymer;
mixing the modified plant fiber and the modified thermoplastic polymer, and spinning to obtain a composite fiber;
sequentially carrying out dust removal, carding and lapping, needle punching to form a felt, hot press molding and edge sealing treatment on the composite fiber to obtain a plant fiber reinforced thermoplastic polymer composite material;
the auxiliary agent comprises an odor adsorbent, a mildew inhibitor, a flame retardant, an anti-wear agent and an interfacial compatilizer.
2. The method according to claim 1, wherein the plant fiber comprises one or more of bamboo fiber, hemp fiber, wood fiber, cotton fiber, straw fiber, coconut fiber, and banana fiber.
3. The preparation method according to claim 1, wherein the interfacial modification comprises impregnation modification or in-situ modification; the modifier used for the immersion modification comprises KH550, nano calcium carbonate, nano titanium dioxide or polydopamine; the modifiers used for the in-situ modification are calcium chloride and sodium carbonate.
4. The method of claim 1, wherein the thermoplastic polymer comprises one or more of polyamide, polypropylene, polycarbonate, acrylonitrile butadiene styrene, polyethylene terephthalate, polybutylene terephthalate, polyoxymethylene, and polylactic acid.
5. The method of claim 1, wherein the odor adsorbent comprises a physical adsorbent and/or a chemical adsorbent; the physical adsorbent comprises a clay material, porous calcium silicate or zeolite; the chemical adsorbent comprises rosin ester, zinc ricinoleate, vinyl POSS modified nanoparticles or methyl propenyl POSS modified nanoparticles.
6. The production method according to claim 1, wherein the mildewcide includes a primary mildewcide and a synergistic mildewcide; the main mildew preventive comprises chitosan, cassia oil, allicin, camphor powder or zinc borate; the synergistic mildew preventive comprises zinc oxide, cuprous oxide, nano silver, nano titanium dioxide, quaternary ammonium salt or o-phenylphenol; the content ratio of the main mildew preventive and the synergistic mildew preventive in the thermoplastic polymer is (1-5) wt% to (0-3) wt%; the interfacial compatilizer is maleic anhydride grafted compatilizer, and the interfacial compatilizer comprises maleic anhydride grafted polyolefin, maleic anhydride grafted POE or maleic anhydride grafted SEBS.
7. The preparation method according to any one of claims 1 to 6, wherein the mass percentages of the odor adsorbent, the mildew inhibitor, the flame retardant, the wear-resistant agent and the interfacial compatilizer in the thermoplastic polymer are 1 to 10 wt%, 1 to 8 wt%, 5 to 30 wt%, 1 to 20 wt% and 1 to 5 wt% in sequence; and the mass contents of the modified plant fiber and the thermoplastic polymer are 25-65 wt% and 35-75 wt% in sequence, wherein the total mass content of the modified plant fiber and the thermoplastic polymer is 100%.
8. The method according to claim 1, wherein the hot press forming temperature is 180 to 230 ℃, the pressure is 0.5 to 5.0MPa, and the time is 2 to 20 min.
9. The plant fiber reinforced thermoplastic polymer composite material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the plant fiber reinforced thermoplastic polymer composite of claim 9 in automotive interior materials.
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