CN114045043A - High-impact wood-plastic helmet composite material and preparation method thereof - Google Patents
High-impact wood-plastic helmet composite material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention belongs to the field of composite materials, and relates to a high-impact wood-plastic helmet composite material and a preparation method thereof. The wood long fiber is subjected to secondary pretreatment, so that the structure of the wood long fiber which is dispersed in advance is reserved, and the wood long fiber is easy to disperse; further utilizing a double-stage double-screw extruder, and utilizing the first-stage screw extruder to fully melt the ABS system; the second-stage screw extruder disperses the wood long fiber subjected to secondary treatment with the ABS system, so that the wood long fiber is efficiently dispersed in the ABS system, the long fiber is completely reserved, and long fiber damage caused by over-shearing is avoided. The obtained wood-plastic helmet composite material wood long fiber wood is mutually crossed and intertwined, has a good reinforcing effect, and has an obvious improvement on the shock resistance.
Description
Technical Field
The invention relates to the field of functional polymer materials, in particular to the field of composite materials for helmet shells, and particularly relates to a high-impact wood-plastic helmet composite material and a preparation method thereof.
Background
With the propulsion of a helmet and a belt, the safety helmet becomes an indispensable requirement of a motorcycle, a bicycle and an electric bicycle. And the helmet is greatly used on various pulleys, balance cars and sliding plates, so that the demand on the helmet is rapidly increased. Because of the characteristic of easy processing and forming of plastic, the conventional helmet is mainly made of plastic, and the structure of the helmet comprises an outer shell, a buffer layer lining, a suspension device and the like. The shell is generally made of hard plastics such as ABS and the like with good abrasion resistance and compression resistance. ABS is an acrylonitrile-butadiene-styrene copolymer, which aggregates the rigidity of polyacrylonitrile and the impact resistance of polybutadiene, and is currently the preferred material for most helmet shells. The outer layer of the helmet is required to have high hardness, wear resistance, difficult deformation, good rigidity, difficult fracturing and higher impact resistance, so that the helmet can well prevent deformation and cracking during impact to protect the head.
When ABS is actually selected to manufacture the helmet shell, the balance between rigidity and impact resistance of raw materials is difficult to achieve. ABS which is often higher in rigidity has poorer toughness and impact resistance and is easy to crack.
In order to improve the impact resistance of ABS, which has toughness and impact resistance at the same time, the prior art adopts an alloy mode to improve ABS. For example, the toughness and impact resistance of the alloy material are greatly improved by adding PA into ABS.
The impact resistance of ABS is also improved by carbon fiber and glass fiber. Chinese patent publication No. CN109867904B discloses a carbon fiber reinforced ABS composite material and a preparation method thereof. The method adopts long carbon fibers, and introduces the long carbon fibers to be forcedly impregnated when the ABS is melted, so that the carbon fibers in the carbon fiber reinforced ABS composite material keep the length. According to related tests, the notch impact strength of the carbon fiber reinforced ABS cantilever beam can be improved by more than 150%. The carbon fiber is extremely remarkable in increasing the impact resistance of ABS. However, the cost of carbon fiber is high, and more than 20% of carbon fiber used for ABS causes a significant increase in cost.
The wood fiber is a natural fiber which is easy to obtain, has the reinforcing and toughening properties of the fiber, is low in cost and ecological and environment-friendly as the natural biological fiber, and can be used for preparing the helmet shell material by using the wood fiber in the ABS, so that the use amount of the ABS can be greatly reduced, and the carbon emission reduction is of great significance.
For a long time, wood powder, rice hull powder and other wood materials are used as wood-plastic materials for reducing the cost, such as PP, PE, PVC and the like after simple thinning treatment and surface coupling modification treatment, and are used for producing various wood-plastic composite floors, decorative wall panels, decorative frames, stair handrails and the like.
Chinese patent CN105482480A discloses a bamboo fiber reinforced thermoplastic plastic, which is prepared by mixing the following raw materials in parts by weight: 30-60 parts of bamboo fiber, 30-80 parts of thermoplastic plastic, 0.25-0.6 part of coupling agent, 0.3-0.8 part of cross-linking agent and 0.5-1.5 parts of lubricating agent.
The wood fiber is used for preparing the composite material by ABS and used for the shell material of the helmet, although the cost is reduced, the performance is improved to a limited extent, and the impact strength is reduced even when the addition amount of the wood fiber is more than 20 percent.
The reason for this is that wood flour is usually refined to about 100 mesh for dispersing wood flour, and this refinement of wood flour breaks the long fiber structure of wood flour, making it difficult to achieve a highly efficient reinforcing effect in plastics. If the wood fiber with the long fiber structure can be dispersed in the plastic, the significance for upgrading the performance of the existing wood-plastic product is great.
For this reason, we wish to maintain a good wood fiber long fiber structure for treating ABS to obtain a high impact wood plastic composite satisfying the requirements of helmet shells.
Disclosure of Invention
The wood fiber is compounded with ABS in the form of long fiber, which not only can reduce the cost, but also can improve the impact resistance of the material. The material for the helmet can improve the impact resistance. However, how to effectively disperse and combine the wood fiber of the long fiber in the ABS system is a technical problem at present. Aiming at the problem, the invention provides a high-impact wood-plastic helmet composite material, which is prepared by performing secondary treatment on wood long fibers, fully melting an ABS system by using a double-stage double-screw extruder, and dispersing the wood long fibers subjected to secondary treatment, so that the wood long fibers are efficiently dispersed in the ABS system, the long fibers are completely reserved, the damage of the long fibers caused by over-shearing is avoided, and the obtained wood-plastic helmet composite material has excellent impact resistance. Further provides a preparation method of the high impact wood plastic helmet composite material.
In order to realize the beneficial effects, the invention adopts the following specific technical scheme:
firstly, a preparation method of a high-impact wood-plastic helmet composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding the wood long fiber, the coupling agent, the dispersing agent and the micron-sized spherical inorganic filler into a stirrer, stirring and dispersing at low speed for 5-15min at 80-120 ℃ and at the rotating speed of 20-30rpm, and discharging to obtain primary treatment wood long fiber powder;
(2) mixing the first-stage treated wood long fiber obtained in the step (1) with a styrene-butadiene-styrene block copolymer according to the mass ratio of 3: 2 heating to 190 ℃ in a kneading machine, kneading for 3-5min, discharging in an open mill, discharging sheets while the sheets are hot, cooling, folding and stacking to obtain sheets of the secondary-treated wood long fibers;
(3) adding ABS, a compatilizer, an antioxidant, a flame retardant and a processing aid into a high-speed mixer, uniformly mixing, extruding by a first-stage double-screw extruder of a double-stage double-screw extruder to obtain a molten material, when the molten material enters a second-stage double-screw extruder, cutting the wood long fiber sheet material subjected to secondary treatment in the step (2) into strips with the width of 3-5cm, feeding the strips and the molten material into the second-stage double-screw extruder, forming the strips by a die head of the extruder, and feeding the strips to a chain for air cooling and a hobbing cutter for pelletizing to obtain the high-impact wood-plastic helmet composite material; wherein, the first-stage double-screw extruder of the double-stage double-screw extruder is a co-rotating double-screw extruder, and the length-diameter ratio is 36-48; the second-stage double-screw extruder of the double-stage double-screw extruder is a counter-rotating double-screw extruder, and the length-diameter ratio is 10-15; the length of the material strips granulated by the hobbing cutter is 1 cm.
Preferably, the wood long fiber, the coupling agent, the dispersing agent and the micron-sized spherical inorganic filler in the step (1) are mixed according to a mass ratio of 100: 1-2: 2-3: 3-5, mixing.
Preferably, the wood long fiber in the step (1) is at least one of flax, sisal, kenaf, jute and bamboo fiber; the length of the long wood fiber is 5-15mm, and the length-diameter ratio of the long wood fiber is more than or equal to 20. The wood long fiber has a longer fiber length and a higher length-diameter ratio, and the impact resistance effect of the composite material is improved obviously.
Preferably, the coupling agent in step (1) is at least one of an aluminate coupling agent and a silane coupling agent.
Preferably, the dispersant in step (1) is at least one selected from stearic acid, polyethylene wax, ethylene bis stearamide, stearic acid amide and stearic acid mono-anhydride ester.
Preferably, the micron-sized spherical inorganic filler in the step (1) is spherical inorganic powder with the sphericity of more than 0.80 and the particle size of 20-50 μm. Such as spherical barium sulfate and spherical glass beads. The micron-sized spherical inorganic filler can prevent the long fibers dispersed in the stirrer from being entangled and agglomerated during the treatment of the wood long fibers.
Preferably, the kneader in the step (2) is a horizontal kneader, the rotation speed of the kneader is 10-15rpm, and the kneader melts the styrene-butadiene-styrene block copolymer and effectively blends the styrene-butadiene-styrene block copolymer with the wood long fiber under the conditions of low rotation speed and low shear; the styrene-butadiene-styrene block copolymer (SBS) has excellent toughness and impact resistance, requires a low shear rate during processing, and can be melted without excessive shear to be blended and dispersed with the wood long fiber.
Preferably, the thickness of the open mill sheet in the step (2) is controlled to be 10-15 mm.
Preferably, the ABS, the compatilizer, the antioxidant, the flame retardant and the processing aid in the step (3) are mixed according to a mass ratio of 100:2-3:0.1-0.2: 1-3: 0.1-0.2 ingredient.
Preferably, the compatilizer in the step (3) is a polymer grafted by maleic anhydride.
Preferably, the antioxidant in the step (3) is at least one of an antioxidant 1010 and an antioxidant 168.
Preferably, at least one of decabromodiphenyl ether and tetrabromobisphenol A is used as the flame retardant in the step (3).
Preferably, the processing aid in the step (3) is a fluoropolymer for improving processing fluidity and surface smoothness when the composite material is used for injection molding of the helmet. Further preferred is PPA-ST3300 available from Seito Polymer materials, Inc.
Preferably, the wood long fiber flakes subjected to secondary treatment in the step (3) and the molten material enter a second-stage twin-screw extruder together according to the mass ratio of 1: 1, feeding.
Preferably, the temperature of the first-stage twin-screw extruder of the two-stage twin-screw extruder in the step (3) is 220 ℃ and 230 ℃, and the screw rotating speed is 220rpm and 250 rpm.
Preferably, the temperature of the second-stage twin-screw extruder of the two-stage twin-screw extruder in the step (3) is 200 ℃ to 230 ℃, and the screw rotating speed is 60-80 rpm.
When the wood long fiber is dispersed in the ABS, the viscosity of the ABS during hot melting is high, the wood fiber can be dispersed in the ABS only by strong shearing dispersion, and the strong shearing can cause the wood long fiber to be excessively sheared and shortened, thereby influencing the reinforcing effect. In order to solve the problem, the invention carries out secondary treatment on the wood long fiber. Firstly, the surface of the fiber is treated by using a coupling agent, low stirring is adopted for preventing long fiber from winding and agglomerating, and a certain amount of micron-sized spherical inorganic filler is added for dispersing; in the second-stage treatment, the first-stage treated wood long fiber is dispersed in styrene-butadiene-styrene block copolymer (SBS), the SBS has excellent toughness and impact resistance, the required shearing rate is low during processing, and the wood long fiber can be dispersed in the SBS system through low-shear kneading of a kneader. The wood long fiber is dispersed by the secondary dispersion treatment, and the characteristics of the long fiber are kept.
More importantly, the wood long fiber subjected to secondary treatment does not need to be sheared and dispersed with ABS for a long time, the first-stage double-screw extruder adopting the double-stage double-screw extruder is a homodromous high-length-diameter-ratio screw, an ABS system is sheared and dispersed strongly to obtain a molten material, when the molten material enters the second-stage double-screw extruder, the second-stage double-screw extruder is a counter-rotating double-screw extruder, the length-diameter ratio is low, the shearing strength is low, the mixing effect is good, the wood long fiber subjected to secondary treatment is mixed and dispersed in the ABS system, and therefore the damage of screw shearing to the long fiber is reduced greatly. And when the hobbing cutter is used for pelletizing, the length of the material strip is 1cm, so that long fibers are well reserved in the material strip.
Furthermore, the invention provides the high-impact wood-plastic helmet composite material prepared by the method. The remarkable technical innovation points are as follows: the wood long fiber is subjected to secondary treatment, so that the structure of the wood long fiber which is dispersed in advance is reserved, and the wood long fiber is easy to disperse; further utilizing a double-stage double-screw extruder, and utilizing the first-stage screw extruder to fully melt the ABS system; the second-stage screw extruder disperses the wood long fiber subjected to secondary treatment with the ABS system, so that the wood long fiber is efficiently dispersed in the ABS system, the long fiber is completely reserved, and long fiber damage caused by over-shearing is avoided. The wood fiber content of the obtained wood-plastic helmet composite material exceeds 20%, the helmet shell is prepared by injection molding, the wood long fiber wood is mutually crossed and intertwined, the helmet shell has a good reinforcing effect, and the impact resistance is obviously improved.
Compared with the prior art, the high-impact wood-plastic helmet composite material and the preparation method thereof have the following beneficial effects:
(1) the long fiber is retained by the primary treatment of low-speed stirring of the wood long fiber and the secondary treatment of kneading with SBS, and the long fiber has the property of easy dispersion.
(2) The ABS system is subjected to strong shearing, dispersion and melting by adopting a double-stage double-screw extruder in the first-stage double-screw extruder, and the wood long fiber subjected to secondary treatment is mixed and dispersed in the ABS system when entering the second-stage double-screw extruder, so that the damage of screw shearing to the long fiber is reduced. The impact resistance of the ABS can be effectively improved.
(3) The preparation method is simple in preparation process, does not need special equipment, and is suitable for industrial large-scale production.
In conclusion, the technical scheme of the invention has outstanding characteristics and obvious practical value, and no related publicly published technology exists in the products in the prior art, thereby having obvious progress compared with the prior art and wide large-scale popularization and production values.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the technical idea of the present invention is shown in the following schematic process flow diagram.
FIG. 1: the preparation method of the invention has a process flow chart.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions 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 embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
(1) Adding 50kg of flax fiber with the length of 5-15mm and the length-diameter ratio of more than or equal to 20, 1kg of aluminate coupling agent, 1kg of stearic acid and 2.5kg of spherical barium sulfate with the sphericity of more than 0.80 and the particle size of 20-50 mu m into a stirrer, stirring and dispersing at low speed for 10min at the rotating speed of 20rpm at 100 ℃, discharging to obtain primary treatment wood long fiber powder;
(2) mixing the first-stage treated wood long fiber obtained in the step (1) with a styrene-butadiene-styrene block copolymer (Qimei SBS PB-5910) according to the mass ratio of 3: 2 heating the mixture in a kneader to 190 ℃, kneading the mixture for 5min at the rotating speed of 15rpm, discharging the mixture in an open mill, discharging the mixture while the mixture is hot, controlling the thickness of the discharged mixture to be 10mm, and cooling and folding the mixture to stack the mixture to obtain second-stage treated wood long fiber sheets for later use;
(3) 50kg of ABS (Qimei PA747), 1.5kg of SEBS-G-MAH (the brand number Kraton G1901X), 10100.08kg of antioxidant, 0.02kg of antioxidant, 1kg of decabromodiphenyl ether and 0.1kg of PPA-ST3300 (provided by Setaria polymer materials company) are added into a high-speed mixer to be uniformly mixed, and then the mixture is extruded by a first-stage double-screw extruder of a two-stage double-screw extruder, wherein the first-stage double-screw extruder is a co-rotating double-screw extruder, the length-diameter ratio is 48, the extrusion temperature is 230 ℃, and the screw rotation speed is 250 rpm; when entering a second-stage double-screw extruder, cutting the wood long fiber sheet material processed in the second stage in the step (2) into strips with the width of 5cm, and mixing the strips with the molten material according to the mass ratio of 1: 1, feeding; entering a second-stage double-screw extruder, wherein the second-stage double-screw extruder is a counter-rotating double-screw extruder, the length-diameter ratio is 10, the temperature of the extruder is 220 ℃, and the rotating speed of screws is 60 rpm; and (3) forming strips through a die head of an extruder, sending the strips to a chain for air cooling, cutting the strips into granules by a hob, wherein the length of the strips is 1cm, and thus the high-impact wood-plastic helmet composite material is prepared.
Example 2
(1) Adding 50kg of bamboo fiber with the length of 5-15mm and the length-diameter ratio of more than or equal to 20, 1kg of silane coupling agent, 1.5kg of polyethylene wax, 2.5kg of spherical glass beads with the sphericity of more than 0.80 and the particle size of 20-50 mu m into a stirrer, stirring and dispersing at low speed for 15min at the temperature of 120 ℃ and the rotating speed of 30rpm, and discharging to obtain primary-treated wood long fiber powder;
(2) mixing the first-stage treated wood long fiber obtained in the step (1) with a styrene-butadiene-styrene block copolymer (Qimei SBS PB-5910) according to the mass ratio of 3: 2 heating the mixture in a kneader to 190 ℃, kneading the mixture for 3min at the rotating speed of 10rpm, discharging the mixture in an open mill, discharging the mixture while the mixture is hot, controlling the thickness of the discharged mixture to be 10mm, and cooling and folding the mixture to stack the mixture to obtain second-stage treated wood long fiber sheets for later use;
(3) 50kg of ABS (Qimei PA747), 1.5kg of SEBS-g-MAH (brand Taftec M)), 10100.08kg of antioxidant, 1680.02 kg of antioxidant, 1kg of flame retardant decabromodiphenyl ether, 0.5kg of tetrabromobisphenol A and 0.1kg of PPA-ST3300 (provided by Seito high polymer materials company) are added into a high-speed mixer to be uniformly mixed, and the mixture is extruded by a first-stage double-screw extruder of a double-stage double-screw extruder, wherein the first-stage double-screw extruder is a co-rotating double-screw extruder, the length-diameter ratio is 48, the extrusion temperature is 230 ℃, and the screw rotation speed is 220 rpm; when entering a second-stage double-screw extruder, cutting the wood long fiber sheet material processed in the second stage in the step (2) into strips with the width of 3cm and molten materials according to the mass ratio of 1: 1, feeding materials, feeding the materials into a second-stage double-screw extruder, wherein the second-stage double-screw extruder is a counter-rotating double-screw extruder, the length-diameter ratio is 10, the temperature of the extruder is 230 ℃, and the rotating speed of screws is 80 rpm; and (3) forming strips through a die head of an extruder, sending the strips to a chain for air cooling, cutting the strips into granules by a hob, wherein the length of the strips is 1cm, and thus the high-impact wood-plastic helmet composite material is prepared.
Example 3
(1) Adding 50kg of sisal fibers with the length of 5-15mm and the length-diameter ratio of more than or equal to 20, 1kg of aluminate coupling agent, 1kg of stearic acid and 2.5kg of spherical barium sulfate with the sphericity of more than 0.80 and the particle size of 20-50 mu m into a stirrer, stirring and dispersing at low speed for 10min at the rotating speed of 20rpm at 100 ℃, discharging to obtain first-stage treated wood long fiber powder;
(2) mixing the first-stage treated wood long fiber obtained in the step (1) with a styrene-butadiene-styrene block copolymer (Qimei SBS PB-5910) according to the mass ratio of 3: 2 heating the mixture in a kneader to 190 ℃, kneading the mixture for 5min at the rotating speed of 15rpm, discharging the mixture in an open mill, discharging the mixture while the mixture is hot, controlling the thickness of the discharged mixture to be 10mm, and cooling and folding the mixture to stack the mixture to obtain second-stage treated wood long fiber sheets for later use;
(3) 50kg of ABS (Qimei PA747), 1.5kg of SEBS-G-MAH (the brand number Kraton G1901X), 10100.08kg of antioxidant, 0.02kg of antioxidant, 1kg of decabromodiphenyl ether and 0.1kg of PPA-ST3300 (provided by Setaria polymer materials company) are added into a high-speed mixer to be uniformly mixed, and then the mixture is extruded by a first-stage double-screw extruder of a two-stage double-screw extruder, wherein the first-stage double-screw extruder is a co-rotating double-screw extruder, the length-diameter ratio is 48, the extrusion temperature is 230 ℃, and the screw rotation speed is 250 rpm; when entering a second-stage double-screw extruder, cutting the wood long fiber sheet material processed in the second stage in the step (2) into strips with the width of 5cm, and mixing the strips with the molten material according to the mass ratio of 1: 1, feeding the materials into a second-stage double-screw extruder, wherein the second-stage double-screw extruder is a counter-rotating double-screw extruder, the length-diameter ratio is 12, the temperature of the extruder is 220 ℃, and the rotating speed of screws is 60 rpm; and (3) forming strips through a die head of an extruder, sending the strips to a chain for air cooling, cutting the strips into granules by a hob, wherein the length of the strips is 1cm, and thus the high-impact wood-plastic helmet composite material is prepared.
Comparative example 1
(1) Adding 50kg of flax fiber with the length of 5-15mm and the length-diameter ratio of more than or equal to 20, 1kg of aluminate coupling agent, 1kg of stearic acid and 2.5kg of spherical barium sulfate with the sphericity of more than 0.80 and the particle size of 20-50 mu m into a stirrer, stirring and dispersing at low speed for 10min at the rotating speed of 20rpm at 100 ℃, discharging to obtain primary treatment wood long fiber powder;
(2) mixing the first-stage treated wood long fiber obtained in the step (1) with a styrene-butadiene-styrene block copolymer (Qimei SBS PB-5910) according to the mass ratio of 3: 2 heating the mixture in a kneader to 190 ℃, kneading the mixture for 5min at the rotating speed of 15rpm, discharging the mixture in an open mill, discharging the mixture while the mixture is hot, controlling the thickness of the discharged mixture to be 10mm, and cooling and folding the mixture to stack the mixture to obtain second-stage treated wood long fiber sheets for later use;
(3) adding 50kg of ABS (Qimei PA747), 1.5kg of SEBS-G-MAH (the trademark Kraton G1901X), 10100.08kg of antioxidant, 0.02kg of antioxidant, 1kg of decabromodiphenyl ether and 0.1kg of PPA-ST3300 (provided by Setaria polymer materials company) into a high-speed mixer, uniformly mixing to obtain a mixture, cutting the two-stage treated wood long fiber sheet into strips with the width of 5cm, and mixing with the mixture according to the mass ratio of 1: 1, feeding the materials through a co-rotating double-screw extruder, wherein the length-diameter ratio is 48, the extrusion temperature is 230 ℃, and the screw rotation speed is 250 rpm; and (3) forming strips through a die head of an extruder, sending the strips to a chain for air cooling, cutting the strips into granules by a hob, wherein the length of the strips is 1cm, and thus the high-impact wood-plastic helmet composite material is prepared.
Comparative example 2
(1) Adding 50kg of flax fiber with the length of 5-15mm and the length-diameter ratio of more than or equal to 20, 1kg of aluminate coupling agent and 1kg of stearic acid into a stirrer, stirring and dispersing at low speed for 10min at the rotating speed of 20rpm at 100 ℃, and discharging to obtain primary-treated wood long fiber powder;
(2) mixing the first-stage treated wood long fiber obtained in the step (1) with a styrene-butadiene-styrene block copolymer (Qimei SBS PB-5910) according to the mass ratio of 3: 2 heating the mixture in a kneader to 190 ℃, kneading the mixture for 5min at the rotating speed of 15rpm, discharging the mixture in an open mill, discharging the mixture while the mixture is hot, controlling the thickness of the discharged mixture to be 10mm, and cooling and folding the mixture to stack the mixture to obtain second-stage treated wood long fiber sheets for later use;
(3) 50kg of ABS (Qimei PA747), 1.5kg of SEBS-G-MAH (the brand number Kraton G1901X), 10100.08kg of antioxidant, 0.02kg of antioxidant, 1kg of decabromodiphenyl ether and 0.1kg of PPA-ST3300 (provided by Setaria polymer materials company) are added into a high-speed mixer to be uniformly mixed, and then the mixture is extruded by a first-stage double-screw extruder of a two-stage double-screw extruder, wherein the first-stage double-screw extruder is a co-rotating double-screw extruder, the length-diameter ratio is 48, the extrusion temperature is 230 ℃, and the screw rotation speed is 250 rpm; when entering a second-stage double-screw extruder, cutting the wood long fiber sheet material processed in the second stage in the step (2) into strips with the width of 5cm, and mixing the strips with the molten material according to the mass ratio of 1: 1, feeding the materials into a second-stage double-screw extruder, wherein the second-stage double-screw extruder is a counter-rotating double-screw extruder, the length-diameter ratio is 10, the temperature of the extruder is 220 ℃, and the rotating speed of screws is 60 rpm; and (3) forming strips through a die head of an extruder, sending the strips to a chain for air cooling, cutting the strips into granules by a hob, wherein the length of the strips is 1cm, and thus the high-impact wood-plastic helmet composite material is prepared.
Comparative example 3
(1) Adding 50kg of flax fiber with the length of 5-15mm and the length-diameter ratio of more than or equal to 20, 1kg of aluminate coupling agent, 1kg of stearic acid and 2.5kg of spherical barium sulfate with the sphericity of more than 0.80 and the particle size of 20-50 mu m into a stirrer, stirring and dispersing at low speed for 10min at the rotating speed of 20rpm at 100 ℃, discharging to obtain primary treatment wood long fiber powder;
(2) mixing the first-stage treated wood long fiber obtained in the step (1) with a styrene-butadiene-styrene block copolymer (Qimei SBS PB-5910) according to the mass ratio of 3: 2, uniformly mixing to obtain second-stage treated wood long fiber sheet stock for later use;
(3) 50kg of ABS (Qimei PA747), 1.5kg of SEBS-G-MAH (the brand number Kraton G1901X), 10100.08kg of antioxidant, 0.02kg of antioxidant, 1kg of decabromodiphenyl ether and 0.1kg of PPA-ST3300 (provided by Setaria polymer materials company) are added into a high-speed mixer to be uniformly mixed, and then the mixture is extruded by a first-stage double-screw extruder of a two-stage double-screw extruder, wherein the first-stage double-screw extruder is a co-rotating double-screw extruder, the length-diameter ratio is 48, the extrusion temperature is 230 ℃, and the screw rotation speed is 250 rpm; and (3) when entering a second-stage double-screw extruder, mixing the secondary-stage treated wood long fiber material in the step (2) with the molten material according to the mass ratio of 1: 1, feeding the materials into a second-stage double-screw extruder, wherein the second-stage double-screw extruder is a counter-rotating double-screw extruder, the length-diameter ratio is 10, the temperature of the extruder is 220 ℃, and the rotating speed of screws is 60 rpm; and (3) forming strips through a die head of an extruder, sending the strips to a chain for air cooling, cutting the strips into granules by a hob, wherein the length of the strips is 1cm, and thus the high-impact wood-plastic helmet composite material is prepared.
The performance evaluation was performed on the high impact wood plastic helmet composite obtained in the above examples 1 to 3 and comparative examples 1 to 3 (reference sample is pure ABS (qimei PA 747):
1. impact resistance: the high impact wood plastic helmet composite materials obtained in examples 1-3 and comparative examples 1-3 were dried at 100 ℃ for 1 hour, and then injection molded at 230 ℃. The impact strength was tested in reference to GB/T1843, as shown in Table 1.
2. According to the test of GB/T1040 plastic tensile property test method, the injection molding cutting standard sample is tested for tensile strength, the test speed is 20mm/min, and the test results are shown in Table 1.
Table 1:
through the tests and comparative analysis, the technical scheme of the invention retains the long fiber through the primary treatment of low-speed stirring of the wood long fiber and the secondary treatment of kneading with SBS, and has the performance of easy dispersion. The ABS system is subjected to strong shearing, dispersion and melting by adopting a double-stage double-screw extruder in the first-stage double-screw extruder, and the wood long fiber subjected to secondary treatment is mixed and dispersed in the ABS system when entering the second-stage double-screw extruder, so that the damage of screw shearing to the long fiber is reduced. The impact resistance of the ABS can be effectively improved.
In the implementation of the comparative example 1, ABS is not pre-melted, but is directly mixed with the wood long fiber flakes subjected to secondary treatment in a co-rotating twin-screw extruder, and under the influence of screw shearing, the long fibers are sheared and damaged more, so that the impact resistance increasing effect of the long fibers in the composite material is avoided, and the impact resistance is reduced.
In the implementation of the comparative example 2, no spherical barium sulfate is added when the wood long fiber is subjected to primary treatment, and the long fiber is wound and agglomerated more when the surface treatment is carried out by stirring, so that the subsequent dispersion of the long fiber is influenced, and the improvement of the impact resistance of the composite material is limited.
Comparative example 3 in practice, the first-stage treated long wood fibers were directly mixed with the styrene-butadiene-styrene block copolymer without preliminary kneading and dispersion when the long wood fibers were subjected to the second-stage treatment, and although the long fibers remained intact in the final composite, the dispersion thereof in the second-stage screw was limited because of the absence of preliminary dispersion of SBS for the long fibers, resulting in a large amount of stacking and agglomeration of the long fibers in the composite and a decrease in impact resistance of the composite.
Claims (10)
1. A preparation method of a high-impact wood-plastic helmet composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding the wood long fiber, the coupling agent, the dispersing agent and the micron-sized spherical inorganic filler into a stirrer, stirring and dispersing at low speed for 5-15min at 80-120 ℃ and at the rotating speed of 20-30rpm, and discharging to obtain primary treatment wood long fiber powder;
(2) mixing the first-stage treated wood long fiber obtained in the step (1) with a styrene-butadiene-styrene block copolymer according to the mass ratio of 3: 2 heating to 190 ℃ in a kneading machine, kneading for 3-5min, discharging in an open mill, discharging sheets while the sheets are hot, cooling, folding and stacking to obtain sheets of the secondary-treated wood long fibers;
(3) adding ABS, a compatilizer, an antioxidant, a flame retardant and a processing aid into a high-speed mixer, uniformly mixing, extruding by a first-stage double-screw extruder of a double-stage double-screw extruder to obtain a molten material, when the molten material enters a second-stage double-screw extruder, cutting the wood long fiber sheet material subjected to secondary treatment in the step (2) into strips with the width of 3-5cm, feeding the strips and the molten material into the second-stage double-screw extruder, forming the strips by a die head of the extruder, and feeding the strips to a chain for air cooling and a hobbing cutter for pelletizing to obtain the high-impact wood-plastic helmet composite material; wherein, the first-stage double-screw extruder of the double-stage double-screw extruder is a co-rotating double-screw extruder, and the length-diameter ratio is 36-48; the second-stage double-screw extruder of the double-stage double-screw extruder is a counter-rotating double-screw extruder, and the length-diameter ratio is 10-15; the length of the material strips granulated by the hobbing cutter is 1 cm.
2. The preparation method of the high impact wood plastic helmet composite material according to claim 1, characterized in that: the wood long fiber, the coupling agent, the dispersing agent and the micron-sized spherical inorganic filler in the step (1) are mixed according to the mass ratio of 100: 1-2: 2-3: 3-5, mixing.
3. The preparation method of the high impact wood plastic helmet composite material according to claim 1, characterized in that: the length of the long wood fiber in the step (1) is 5-15mm, the length-diameter ratio of the long wood fiber is more than or equal to 20, and at least one of flax, sisal, kenaf, jute and bamboo fiber is selected; the coupling agent is at least one of an aluminate coupling agent and a silane coupling agent; the dispersing agent is at least one of stearic acid, polyethylene wax, ethylene bis stearamide, stearic acid amide and stearic acid mono-anhydride ester; the micron-sized spherical inorganic filler is spherical inorganic powder with the sphericity of more than 0.80 and the particle size of 20-50 mu m.
4. The preparation method of the high impact wood plastic helmet composite material according to claim 1, characterized in that: the kneader in the step (2) is a horizontal kneader, and the rotating speed of the kneader is 10-15 rpm.
5. The preparation method of the high impact wood plastic helmet composite material according to claim 1, characterized in that: and (3) controlling the thickness to be 10-15mm when the sheet is discharged from the open mill in the step (2).
6. The preparation method of the high impact wood plastic helmet composite material according to claim 1, characterized in that: and (3) ABS, a compatilizer, an antioxidant, a flame retardant and a processing aid in a mass ratio of 100:2-3:0.1-0.2: 1-3: 0.1-0.2 ingredient.
7. The preparation method of the high impact wood plastic helmet composite material according to claim 1, characterized in that: the compatilizer in the step (3) is a polymer grafted by maleic anhydride; the antioxidant is at least one of an antioxidant 1010 and an antioxidant 168; at least one of decabromodiphenyl ether and tetrabromobisphenol A serving as flame retardants; the processing aid is a fluoropolymer.
8. The preparation method of the high impact wood plastic helmet composite material according to claim 1, characterized in that: and (3) when the wood long fiber sheet materials subjected to secondary treatment in the step (3) and the molten materials enter a second-stage double-screw extruder together according to the mass ratio of 1: 1, feeding.
9. The preparation method of the high impact wood plastic helmet composite material according to claim 1, characterized in that: the temperature of the first-stage double-screw extruder of the two-stage double-screw extruder is 220-; the temperature of the second-stage double-screw extruder of the double-stage double-screw extruder is 200 ℃ and 230 ℃, and the screw rotating speed is 60-80 rpm.
10. A high impact wood plastic helmet composite characterized by being prepared by the process of any one of claims 1 to 9.
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| WO2023097950A1 (en) * | 2021-11-30 | 2023-06-08 | 浙江远景体育用品股份有限公司 | High impact-resistant wood-plastic helmet composite material, and preparation method |
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| WO2023097950A1 (en) * | 2021-11-30 | 2023-06-08 | 浙江远景体育用品股份有限公司 | High impact-resistant wood-plastic helmet composite material, and preparation method |
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