CN103937279B - A kind of magnetic wood plastic composite and preparation method thereof - Google Patents
A kind of magnetic wood plastic composite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of magnetic Wood-plastic mix material and preparation method thereof, described material is mainly made up of the raw material of following mass percent: the plastic substrate of 20-40%, the plant powder of 20-40%, the micro-nano magnetic powder of ferrite of 20-50%, the coupling agent of 3-6%, the bulking agent of 0.1-1%, the lubricant of 1-3%, 2 ~ 4% toughener, 0.01 ~ 0.1% peroxide.Described method mainly includes magnetic powder activation, plant powder dries, mixing and molding step is poly-.This magnetic wood plastic composite has not only had plastics and wood material major advantage concurrently, and give wood plastic composite magnetization function, the market multifunction demand to Wood-plastic material can be met, can be widely applied in fields such as teaching aid, advertisement, toy, electronic packaging, extraordinary finishings, there is wide economic outlook and social benefit.
Description
Technical field
The invention belongs to a kind of wood plastic composite field, especially relate to a kind of magnetic wood plastic composite and preparation method thereof.
Background technology
Along with the development of science and technology, modern society is more and more higher to the requirement of material, and it not only should have good physical and mechanical property and eco-environmental prote, but also should meet some special requirements, and namely multifunctionality is the direction of its future development.Magnetic composite, as magnetic Nano microsphere, magnetic timber and magnetic plastics etc. be after 20 century 70s progressively Emergence and Development, growth, and become the NEW TYPE OF COMPOSITE magnetic material being full of vitality most with broad application prospect, not only there is magnetic characteristic, but also there is the multiple specific functions such as humid control, acoustic absorption and electro-magnetic wave absorption, it is with a wide range of applications in fields such as magnetic therapy, religion instrument, electromagnetic shielding, electronic packaging, extraordinary finishings.
Wood plastic composite is to make it with various plastics adhesives by a certain percentage to mix and add a kind of advanced composite material (ACM) that related auxiliaries through techniques such as high temperature, extruding, molding make for primary raw material through suitable activation processing with Plant fiber, is the environmental protection composite of a kind of high-performance, high added value.Compared with wood materials, have that material is homogeneous, be susceptible to advantages such as damaging by worms, water-tolerant, the ratio of strength to weight are high, dimensionally stable is good, easily make variously-shaped pressing；Compared with high molecule plastic, there is low toxicity, Heat stability is good, the advantage such as with low cost.It addition, wood plastic composite can adopt various waste or used plastics, waste wood and annual regeneration crop plant material, it is possible to contribute to alleviating plastic pollution, reduce waste agronomic crop and burn the destruction to environment, be a kind of long life material that can be recycled.Therefore, China's Ecological Civilization Construction will be produced actively impact by the exploitation of Novel wood-plastic composite material.
At present, wood plastic composite is generally used for the fields such as building decoration, Furniture manufacture, garden landscape, article of everyday use, but its function and application also have very big potentiality to dig.Such as new disclosed patent application CN103205059A, disclose the Wood plastic composite of a kind of maskable electromagnetism, the graphite powder playing shielding electromagnetic action is filled and moulds in wood compound, prepare the Wood plastic composite with shielding function solenoid；If wood plastic composite can be carried out magnetization process, it is possible not only to make wood plastic composite possess wood material and the many too late physicochemical properties of plastics and environment-friendly advantage, and wood plastic composite magnetization function can be given, give play to the double dominant of magnetic timber and magnetic plastics, so that Wood-plastic material is extended in more wide application.But yet there are no the open report of magnetic wood plastic composite exploitation aspect, in view of that, the present invention is exactly the NEW TYPE OF COMPOSITE Wood-plastic material prepared and have magnetic function.
Summary of the invention
The present invention is directed to wood plastic composite market multifunction demand and the shortcoming such as existing associated magnetic material cost is high, yielding, easy to crack, dimensionally stable is poor, the preparation method that a kind of Novel wood-plastic composite material with magnetic function is provided, plastics and wood material major advantage are not only had concurrently, and give wood plastic composite magnetization function, it is possible to it is applied in fields such as teaching aid, advertisement, toy, electronic packaging, extraordinary finishings.
For achieving the above object, the present invention is by the following technical solutions:
A kind of magnetic wood plastic composite, it is characterized in that, it is mainly made up of the raw material of following mass percent, the plastic substrate of 20-40%, the plant powder of 20-40%, the micro-nano magnetic powder of ferrite of 20-50%, the coupling agent of 3-6%, the bulking agent of 0.1-1%, the lubricant of 1-3%, 2 ~ 4% toughener, 0.01 ~ 0.1% peroxide etc..
Further, described magnetic wood plastic composite can also add other function additives as required, such as antioxidant, fire retardant, pigment, foaming agent, one or more the combination of anti-microbial inoculum；
Further, described plastic substrate is the combination of one or more in polypropylene, polyethylene, polrvinyl chloride and polystyrene.
Further, the micro-nano magnetic powder of described ferrite is ferroso-ferric oxide (Fe3O4), Barium hexaferrite (BaO 6Fe2O3) and strontium ferrite (SrO 6Fe2O3) in one, particle size range 0.03 ~ 10.0 micron.
Further, described plant powder is all kinds of wood powder, bamboo powder, crop stalk powder, bran powder, shell powder, powder particle size scope 50 ~ 200 order.
Further, described coupling agent is combination at least one or several in titanate coupling agent, silane coupler, aluminate coupling agent or Al-Ti-diffused steel coupling agent.
Further, described lubricant is the one in stearic acid and its esters, Tissuemat E, paraffin, OPE.
Further, described peroxide is at least one in cumyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide or peroxidized t-butyl perbenzoate.
Further, described bulking agent is at least one in maleic anhydride, isocyanates, phthalic anhydride, polymethylene polyphenyl isocyanate.
Further, described toughener is at least one in POE, TPO, EPDM, SBS, SEBS.
The present invention also discloses the method preparing above-mentioned magnetic wood plastic composite, comprise the following steps:
The first step: magnetic micro-nano powder, Polyethylene Glycol (molecular weight is 200 ~ 400) dehydrated alcohol and deionized water are moved in container by magnetic powder activation by a certain percentage, and disperse 10min with ultrasound wave, add coupling agent alcoholic solution, it is warming up to 60 ~ 80 DEG C, constant temperature stir about stands 24h, the elimination supernatant after 2 hours, be placed in air dry oven at 100 DEG C, dry 10h, the magnetic powder filler of activation processing.
Second step: plant powder dries just plant powder and is placed in air dry oven at 105 DEG C and dries 10h, standby to water quality mark < 2%；
3rd step: mixing roll is warming up to the processing temperature of corresponding plastics by mixing process, is typically within the scope of 150 ~ 220 DEG C, is subsequently adding plastics, plastifies 5-15 minute；Add the auxiliary agents such as the dried plant powder in activation magnetic powder, the second step in the first step, toughener, lubricant, bulking agent, peroxide, mix 10-20 minute；
4th step: forming processes can pass through vulcanizing press hot-pressing processing molding, it is also possible to melt extrudes molding by twin screw or single screw extruder.(1) if by vulcanizing press hot-pressing processing molding, directly the material of the high-temperature mixing in the 3rd step can being transferred to hot pressing 20-40 minute, last cooling and shaping in the mould of vulcanizing press, obtain product；(2) if melt extruding molding by screw extruder, insert the mixture in the 3rd step to join twin screw or single screw extruder melt extrudes by mixed material after cold mixer carrying out be cooled to 30 ~ 50 DEG C and obtain composite board, shape then through Vacuum shaping platform, cooling, traction, obtain product after cutting technique.
The magnetic wood plastic composite of the present invention utilizes coupling agent, dispersant and ultrasonic means micro-nano magnetic powder material to carry out fully dispersed and finishing activation processing, it is prevented that the gathering of Magnaglo.The Magnaglo of activation processing, plant fiber powder, polymeric matrix and auxiliary agent are carried out melted compound again and prepares magnetic wood plastic composite.Not only had plastics and wood material major advantage concurrently, and while giving wood plastic composite magnetization function, can overcome magnetic timber yielding, easy to crack, weak to shortcomings such as burn into not easily processing and forming；Also the shortcomings such as magnetic plastics cost is high, dimensionally stable is poor, the feature of environmental protection is poor can also be overcome.The market multifunction demand to Wood-plastic material can be met, can be widely applied to especially in fields such as teaching aid, advertisement, toy, electronic packaging, extraordinary finishings.Its preparation section simple and easy reasonable, less costly, easily operate, be suitable to industrialized production, there is wide economic outlook and social benefit.
Detailed description of the invention
Below in conjunction with implementing example, the present invention is specifically described, it should be pointed out that cited enforcement example is served only for the present invention is further detailed, it is impossible to be interpreted as limiting the scope of the invention.This field and skilled person can make some nonessential improvement and adjustment according to present disclosure, fall within protection scope of the present invention.
A kind of magnetic wood plastic composite, it is by the raw material compositing range of following mass percent: the plastic substrate of 20-40%, the plant powder of 20-40%, the ferromagnetic oxide powder of 20-50%, the coupling agent of 3-6%, the bulking agent of 0.1-1%, the lubricant of 1-3%, 2 ~ 4% toughener, 0.01 ~ 0.1% peroxide etc..It addition, other function additives can also be added as required, such as antioxidant, fire retardant, pigment, foaming agent, one or more the combination of anti-microbial inoculum.
The preparation process of one one kinds of magnetic PP wood plastic composites of embodiment
(1) 100 parts of mean diameters are the strontium ferrite barium dust of 2 μm, 5 parts of Liquid Macrogols by raw material preparation, 250 parts of dehydrated alcohol and 25 parts of deionized waters move in container, and disperse 10min with ultrasound wave, (coupling agent mass content is 20% to add the KH-550 silane coupler alcoholic solution of about 30 parts, ethanol mass content is 72%, water quality content 8%), it is warming up to 60 ~ 80 DEG C, constant temperature stir about stands 24h after 2 hours, the elimination supernatant, it is placed in air dry oven at 100 DEG C, dry 10h, the magnetic powder filler of activation processing.And the Masson Pine powder that 90 parts of mean diameters are 80 orders is placed in air dry oven, at 105 DEG C, dry 10h, standby to water quality mark < 2%；
(2) mixing roll is warming up to 190 DEG C by mixed processing, is subsequently adding 80 parts of polypropylene plastics, plastifies 10 minutes；Again the barium ferrite powder filler of above-mentioned whole activation processing, dried Masson Pine powder, 5 parts of POE elastomers, 3 parts of stearic acid, 2.5 parts of maleic anhydrides, 2.5 parts of cumyl peroxides are added in mixing roll, mix 18 minutes.It is mixed thing again to insert and cold mixer carries out be cooled to 40 DEG C；
(3) mixed material of above-mentioned mixed processing is joined in single screw extrusion machine by material molding, extruder temperature is preferably 190 ~ 230 DEG C, mixed material obtains composite through melt extruding, and obtains magnetic wood-plastic composite panel then through after the sizing of Vacuum shaping platform, cooling, traction, cutting technique.
Composite board width 150mm, the thickness 15mm of the present embodiment formula extrusion, test result is: saturation magnetization 12.221emu.g-1, remanent magnetization is 6.561emu.g-1, hot strength 30.52MPa, MOR 28.89MPa, modulus of elasticity in static bending 3516MPa, shore hardness 85.
The preparation process of 21 kinds of magnetic PE bamboo-plastic composite materials of embodiment
(1) 100 parts of mean diameters are the strontium ferrite powder of 1 μm, 6 parts of Liquid Macrogols by raw material preparation, 250 parts of dehydrated alcohol and 25 parts of deionized waters move in container, and disperse 10min with ultrasound wave, (coupling agent mass content is 20% to add the KH-570 silane coupler alcoholic solution of about 30 parts, ethanol mass content is 72%, water quality content 8%), it is warming up to 75 DEG C, constant temperature stir about stands 24h after 2 hours, the elimination supernatant, it is placed in air dry oven at 100 DEG C, dry 10h, the magnetic powder filler of activation processing.And the bamboo powder end that 95 parts of mean diameters are 100 orders is placed in air dry oven, at 105 DEG C, dry 10h, standby to water quality mark < 2%；
(2) mixing roll is warming up to 180 DEG C by mixed processing, is subsequently adding 90 parts of high-density polyethylene plastics, plastifies 10 minutes；Again the strontium ferrite powder filler of above-mentioned whole activation processing, dried bamboo powder, 6 parts of POE elastomers, 3 parts of stearic acid, 2.5 parts of maleic anhydrides, 2.5 parts of cumyl peroxides are added in mixing roll, mix 18 minutes.It is mixed thing again to insert and cold mixer carries out be cooled to 35 DEG C；
(3) mixed material of above-mentioned mixed processing is joined in single screw extrusion machine by material molding, extruder temperature is preferably 170 ~ 200 DEG C, mixed material obtains composite through melt extruding, and obtains the bamboo-plastic combined sheet material of magnetic PE then through after the sizing of Vacuum shaping platform, cooling, traction, cutting technique.
Composite board width 150mm, the thickness 15mm of the present embodiment formula extrusion, test result is: saturation magnetization 10.451emu.g-1, remanent magnetization is 5.821emu.g-1, hot strength 29.14MPa, MOR 26.21MPa, modulus of elasticity in static bending 3816MPa, shore hardness 82.
31 kinds of magnetic PS of embodiment plant the preparation process of plastic composite materials
(1) 100 parts of mean diameters are the ferroferric oxide magnetic powder of 0.5 μm, 5 parts of Liquid Macrogols by raw material preparation, 250 parts of dehydrated alcohol and 25 parts of deionized waters move in container, and disperse 10min with ultrasound wave, (coupling agent mass content is 25% to add the TC-F titanate coupling agent alcoholic solution of about 30 parts, ethanol mass content is 60%, water quality content 15%), it is warming up to 78 DEG C, constant temperature stir about stands 24h after 2 hours, the elimination supernatant, it is placed in air dry oven at 100 DEG C, dry 10h, the ferroferric oxide magnetic powder filler of activation processing.And the rice straw powder that 85 parts of mean diameters are 100 orders is placed in air dry oven, at 105 DEG C, dry 10h, standby to water quality mark < 2%；
(2) mixing roll is warming up to 170 DEG C by mixed processing, is subsequently adding 85 parts of polystyrene plastics, plastifies 10 minutes；Again the ferroferric oxide magnetic powder filler of above-mentioned whole activation processing, dried rice straw powder, 5 parts of POE elastomers, 3 parts of stearic acid, 2.5 parts of maleic anhydrides, 2.5 parts of cumyl peroxides are added in mixing roll, mix 18 minutes.It is mixed thing again to insert and cold mixer carries out be cooled to 35 DEG C；
(3) mixed material of above-mentioned mixed processing is joined in single screw extrusion machine by material molding, extruder temperature is preferably 170 ~ 200 DEG C, mixed material obtains composite through melt extruding, and plants plastic composite board then through obtaining magnetic PS after the sizing of Vacuum shaping platform, cooling, traction, cutting technique.
Composite board width 150mm, the thickness 15mm of the present embodiment formula extrusion, test result is: saturation magnetization 14.282emu.g-1, remanent magnetization is 7.658emu.g-1, hot strength 27.14MPa, MOR 25.88MPa, modulus of elasticity in static bending 3524MPa, shore hardness 80.
The preparation process of 41 kinds of magnetic PVC wood plastic composite material of embodiment
(1) 100 parts of mean diameters are the ferroferric oxide magnetic powder of 1.0 μm, 6 parts of PEG400s by raw material preparation, 250 parts of dehydrated alcohol and 25 parts of deionized waters move in container, and disperse 10min with ultrasound wave, (coupling agent mass content is 20% to add about 30 parts of JTW-101 titanate coupling agent alcoholic solution, ethanol mass content is 76%, water quality content 4%), it is warming up to 70 DEG C, constant temperature stir about stands 24h after 2 hours, the elimination supernatant, it is placed in air dry oven at 100 DEG C, dry 10h, the magnetic powder filler of activation processing.And the poplar powder that 85 parts of mean diameters are 80 orders is placed in air dry oven, at 105 DEG C, dry 10h, standby to water quality mark < 2%；
(2) mixing roll is warming up to 175 DEG C by mixed processing, is subsequently adding 80 parts of igelites, plastifies 10 minutes；Again the ferroferric oxide magnetic powder filler of above-mentioned whole activation processing, dried wood powder, 6 parts of POE elastomers, 3 parts of stearic acid, 2.5 parts of maleic anhydrides, 2.5 parts of cumyl peroxides are added in mixing roll, mix 20 minutes.
(3) material that above-mentioned high-temperature mixing processes is transferred in the mould of vulcanizing press by material molding, coating releasing agent at mould inner surface, be hot pressing 20 minutes under 10.0MPa at pressure, hot pressing temperature is 180 DEG C, last cooling and shaping, obtains magnetic PVC wood plastic composite board；
Composite board width 150mm, the thickness 15mm of the present embodiment formula extrusion, test result is: saturation magnetization 13.232emu.g-1, remanent magnetization is 5.142emu.g-1, hot strength 26.14MPa, MOR 22.21MPa, modulus of elasticity in static bending 3116MPa, shore hardness is 88.
Claims (7)
1. a magnetic wood plastic composite, it is characterized in that, it is mainly made up of the raw material of following mass percent: the plastic substrate of 20-40%, the plant powder of 20-40%, the micro-nano magnetic powder of ferrite of 20-50%, the coupling agent of 3-6%, the bulking agent of 0.1-1%, the lubricant of 1-3%, 2～4% toughener, 0.01～0.1% peroxide；
The micro-nano magnetic powder of described ferrite is at least one in ferroso-ferric oxide, Barium hexaferrite and strontium ferrite, particle size range 0.03～10.0 micron；Described coupling agent is at least one or several combination in titanate coupling agent, silane coupler, aluminate coupling agent or Al-Ti-diffused steel coupling agent；Described peroxide is at least one in cumyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide or peroxidized t-butyl perbenzoate, and described toughener is at least one in POE, TPO, EPDM, SBS, SEBS；Described bulking agent is at least one in maleic anhydride, isocyanates, phthalic anhydride, polymethylene polyphenyl isocyanate；The activated step process of the micro-nano magnetic powder of described ferrite: by a certain percentage Polyethylene Glycol, dehydrated alcohol and deionized water that micro-nano for described ferrite magnetic powder, molecular weight are 200～400 are moved in container, and disperse 10min with ultrasound wave, add coupling agent alcoholic solution, it is warming up to 60～80 DEG C, constant temperature stands 24h, the elimination supernatant after stirring 2 hours, is placed in air dry oven at 100 DEG C, dry 10h, obtains the micro-nano magnetic powder of ferrite of activation processing.
2. a kind of magnetic wood plastic composite according to claim 1, it is characterised in that also include other function additive, other function additive described is the combination that antioxidant, fire retardant, pigment, foaming agent, anti-microbial inoculum are at least one or several.
3. a kind of magnetic wood plastic composite according to claim 1, it is characterised in that described plastic substrate is at least one or several combination in polypropylene, polyethylene, polrvinyl chloride and polystyrene.
4. a kind of magnetic wood plastic composite according to claim 1, it is characterised in that described plant powder is the one in all kinds of wood powder, bamboo powder, crop stalk powder, bran powder, shell powder, powder particle size scope 50～200 order.
5. a kind of magnetic wood plastic composite according to claim 1, it is characterised in that described lubricant is at least one in stearic acid and its esters, Tissuemat E, paraffin, OPE.
6. the preparation method of the magnetic wood plastic composite according to any claim in claim 1 and 3～5, it is characterised in that mainly comprise the steps that
(1), magnetic powder activation: by a certain percentage Polyethylene Glycol, dehydrated alcohol and deionized water that micro-nano for ferrite magnetic powder, molecular weight are 200～400 are moved in container, and disperse 10min with ultrasound wave, add coupling agent alcoholic solution, it is warming up to 60～80 DEG C, constant temperature stands 24h, the elimination supernatant after stirring 2 hours, is placed in air dry oven at 100 DEG C, dry 10h, obtains the micro-nano magnetic powder of ferrite of activation processing；
(2), plant powder dries: be placed in air dry oven by plant powder at 105 DEG C dry 10h, to water quality mark < 2%, obtains the plant powder dried, standby；
(3), mixing process: mixing roll is warming up to the processing temperature of corresponding plastics, within the scope of 150～220 DEG C, is subsequently adding plastic substrate, plastifies 5-15 minute；Add the dry plant powder described in the micro-nano magnetic powder of ferrite of the activation processing described in step (1), step (2), toughener, lubricant, bulking agent, peroxide, mix 10-20 minute, obtain mixture；
(4), forming processes: melt extrude molding by vulcanizing press hot-pressing processing molding or screw extruder.
7. the preparation method of magnetic wood plastic composite according to claim 6, it is characterized in that, before described step (4) forming processes using screw extruder melt extrude molding, also include cooling and process step: the mixture described in step (3) is inserted and cold mixer carries out be cooled to 30～50 DEG C.
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