A kind of pretreatment process that is applicable to the wood powder of filling plastic
Technical field:
The present invention relates to a kind of pretreatment process of wood powder, be specifically related to the pretreatment process of the wood powder that the production of the polymer composite of a kind of Wood flour filled polypropylene (PP) plastics uses.
Background technology:
Nowadays the plastic industry development rapidly, all be widely used in each field, in order to adapt to different service requirementss, various polyblends, come out one after another with rigid-particle filled polymer composites such as inorganic particle, fibers, and with vegetable fibre filling thermoplastic resins such as wood powder, stalk, rice hulls, by extrude, wood plastic composite (Wood-Plastic Composites, WPC) that the molding mode of the plastics such as injection moulding is processed also with its excellent performance and easily processing mode become one of focus of research.Wood plastic composite is compounded with the characteristics of timber and plastics bi-material, the advantage that can integrate both has been evaded again both some shortcomings, for common timber and plastics, wood plastic composite is drawn materials extensively, and cost is low, again environmental protection, produce wood-plastic products and adopted discarded woodwork scrap stock more, and the reclaimed materials such as wood powder, rice husk meal, stalk, bamboo fibers, paper pulp, greatly reduce cost on the one hand, can save on the other hand the forest reserves of China; Have complementary advantages, comprehensively the advantage of plastics and timber two aspects, both can cut as timber, bondd, punch, and can utilize again the mode of plastic shaping to process, and the product surface that obtains is smooth smooth, can be made into different shape.Simultaneously have again both superiority concurrently on performance, the intensity of existing plastics, water tolerance and insect protected effect have again the high-modulus of timber, low creep and high-dimensional stability.
Wood plastic composite has many advantages, but also has defective, and a greatest problem of restricting current wood plastic composite development is how to make between the surperficial and hydrophobic non-polar plastic substrate interface of hydrophilic polarity vegetable fibre to have good consistency.Cause wood plastic composite particularly can not reach the higher condition of some service requirementss on toughness on mechanical property because consistency is poor, thereby limited the application of wood-plastic products.Therefore will obtain well behaved wood plastic composite must carry out interface modification.
The method of improving the wood plastic composite interface compatibility has a lot, and interface modification method commonly used is mainly that the modes such as coupling agent or compatilizer are processed, added to the pre-treatment of vegetable fibre, resin surface.Wherein used on a large scale coupling agent in the production of wood-plastic products, the coupling agents such as silane system, titanic acid ester system, Aluminate system, titanic acid ester system and isocyanate-based have the use of certain limit; The mode that another kind is widely used is to add compatilizer, comprise maleic anhydride inoculated polypropylene (PP-g-mah), maleic anhydride grafted polyethylene (PE-g-mah), maleic anhydride grafted ethene-octene copolymer (POE-g-mah) etc., the elastomericss such as the Ethylene-Propylene-Diene Monomer (EPDM) of adding (EPDM), styrene-butadiene-styrene (SBS), polyethylene-octene copolymer (POE) are also arranged as plasticized modifier.Compatilizer and coupling agent increase-volume wood plastic composite mechanism comparatively similar, be all to make an end of additive and resin have the good consistency the other end or to produce with the reaction of wood powder surface group to tangle, namely set up cross-linking system between resin and wood powder.
Pre-treatment to wood powder is more to improve the surface group of wood powder or inner the composition, and modal wood powder pretreatment mode is that alkaline purification and surface grafting are processed.Alkaline purification is mainly the lower-molecular substance of removing in wood powder, and it is to introduce the lower group of polarity on the wood powder surface that surface grafting is processed, and the essence of dual mode is all the consistency that the characteristic that changes wood powder improves itself and resin.Expensive coupling agent or compatilizer can not be used in the pre-treatment of wood powder aborning; but from the material property angle; the pretreated effect of wood powder is not as directly adding the effective of coupling agent or compatilizer; and alkaline purification and surface grafting are processed to produce and are polluted waste liquid, are unfavorable for protection of the environment.
Summary of the invention:
The present invention proposes a kind of novel wood powder pretreatment process, do not change by this pretreated wood powder chemical constitution, fibrosis structurally becomes, the wood powder that uses method of the present invention to process, the preparation that is used for the PP base wood-plastic composite material can make matrix material obtain better mechanical property.
The present invention is achieved through the following technical solutions:
A kind of pretreatment process of the wood powder for filling plastic is characterized in that, said method comprising the steps of:
1) boil: wood powder in mass ratio: the ratio of water=1: 5~1: 20, wood powder and water are added in container, the volume of the water yield is less than or equal to 2/3 of container volume; Stir the mixture of wood powder and water until wood powder is sunken to the bottom of container fully, be heated to the water boiling, finish heating after water boiling 5min~60min, wood powder is filtered the wood powder that obtains boiling;
2) pyroprocessing: the wood powder that will boil is placed in vacuum drying oven and carries out the vacuum high-temperature processing in 100~110 ℃, the vacuum keep of baking oven (needn't continue to open vacuum pump at 0.09~0.1MPa in vacuum process, only need reach requirement vacuum tightness gets final product), be full of water vapour in baking oven this moment; Get rid of the water vapour in baking oven after 6~50 hours, wood powder is dried to constant weight under 100~110 ℃, the wood powder that obtains handling well (wood powder is prone to degraded in high-temperature process, and this process is difficult for long).
In wood powder processing mode of the present invention, first wood powder is used water boil in container, be transferred in vacuum drying oven in the pyroprocessing higher than 100 ℃ after removing after filtration most moisture, because baking oven under vacuum state is in airtight state, whole oven interior is full of water vapour, is equivalent to wood powder has been carried out the Saunas processing.The waste water that produces in boiling part contains the water-soluble substances in wood powder, is not harmful waste water, therefore can discharge or reuse.Water-soluble substances in boiling part in wood powder can be precipitated, and the meetings such as some lower-molecular substances such as pectin, half fiber, starch separate with Mierocrystalline cellulose, these lower-molecular substances become gel state gradually in the Saunas treating processes, be conducive to cellulose skeleton structure in wood powder bonding and with the interface of resin bonding, polarizing microscope (POM) photo of wood powder after pyroprocessing as shown in Figure 1, show in photo that untreated wood powder is opaque, and wood powder becomes transparent and obviously is fibrous after treatment.And the wood powder after Saunas is processed has heterogeneous nucleating effect to PP, can improve the degree of crystallinity of PP.The PP that uses requires molecular weight between 50000~1000000, melting index (MFI) 0.5~10g/10min (230 ℃/2.16kg).
The wood powder that use is processed through method of the present invention is used for the preparation of wood plastic composite:
To boil wood powder after processing and PP and add in the HAAKE rheometer and prepare wood plastic composite, prepare wooden plastic sheet material by the compression molding instrument.The mass parts sum of PP and wood powder is defined as 100 parts (phr), and wherein the add-on of wood powder is at 30~70phr, and the add-on of PP is at 30~70phr, and can add in right amount compatilizer, and add-on is advisable at 0~10phr.Wood plastic composite to preparation is tested mechanical property by GB, boil by the analyses such as crystal property and configuration of surface proof and process the consistency that has improved wood powder and PP, and can improve the degree of crystallinity of PP, the mechanical property that improves wood plastic composite has been played double effects.
Beneficial effect
Compare with existing wood powder preconditioning technique, wood powder processing mode of the present invention has the characteristics such as cost is low, processing unit is simple, environmental protection is pollution-free, the matrix material that the wood powder that use is processed through method of the present invention makes, compare with the matrix material of the wood powder preparation of using other modes to process, mechanical property is more superior.Suitable with the composite materials property that adds compatilizer, coupling agent, be fit to suitability for industrialized production.
Description of drawings:
Accompanying drawing 1 is the POM picture of undressed wood powder.
Accompanying drawing 2 is wood powder POM picture after treatment.
Embodiment:
The invention will be further described below in conjunction with embodiment, and its purpose only is better to understand the object of the invention, and unrestricted protection scope of the present invention.
Embodiment 1
Adopt 80 purpose Poplar Powders, jewel bamboo wood powder company limited provides by Linan, Zhejiang; PP, Sinopec Shanghai chemical inc provides, trade mark T300, MFI=3g/10min (2.16KG/230 ℃), the tensile strength of this PP is 31MPa, flexural strength 31MPa, shock strength 9KJ/m
2Directly with electric kettle, wood powder is boiled processing, added wood powder and water than 1: 8 by wood powder and quality, be stirred to and begin heating after wood powder sinks at the bottom of kettle.Boil 10min after water boiling, stopped heating and suction filtration are while hot processed 12h with the wood powder filter cake with vacuum drying oven, and the vacuum tightness of baking oven is at 0.09-0.1MPa.After processing finishes, open the dry wood powder of oven door to constant weight, the then 80 orders processing of sieving.
Wood powder 30phr after processing and PP 70phr and processing aid are added melt blending 15min in the HAAKE rheometer, rotating speed 60rpm, 180 ℃ of blending temperatures; Prepare composite material sheet with 25 tons of compression molding instrument, wherein processing temperature is at 180 ℃, warm up time 12min, hot pressing time 10min, time 8min colds pressing.By national standard test mechanical property, tensile property is tested according to GB/T 1040.2-2006 standard, and bending property is tested according to the GB/T9341-2000 standard, and the performance test of simply supported beam notch shock is according to the GB/T1043-1993 standard.Also contrast according to the mechanical property result PP base wood-plastic composite material that adds the wood powder that is untreated, its tensile strength 32MPa has improved 40%, and flexural strength 41MPa has improved 35%, and modulus in flexure 2300MPa has improved 20%, shock strength 5KJ/m
2Improved 10%, tensile strength and flexural strength have all surpassed the intensity of pure PP.Can be found out the mechanical property that processing has improved Wood-plastic material of boiling of wood powder by result.
Embodiment 2
Adopt 80 purpose Poplar Powders, jewel bamboo wood powder company limited provides by Linan, Zhejiang; PP, Sinopec Shanghai chemical inc provides, trade mark T300; PP-g-mah, Nanjing moral bar chemical industry company limited provide, percentage of grafting approximately 1%.With electric kettle, wood powder is boiled processing, added wood powder and water than 1: 10 by wood powder and quality, be stirred to and begin heating after wood powder sinks at the bottom of kettle.Boil 10min after water boiling, stopped heating and suction filtration while hot carry out Saunas with the wood powder filter cake with vacuum drying oven and process 12h, and the vacuum tightness of baking oven is at 0.09-0.1MPa.After processing finishes, open the dry wood powder of oven door to constant weight, the then 80 orders processing of sieving.
Wood powder 30phr after processing and the PP-g-mah of PP 70phr and 5phr are added melt blending 15min in the HAAKE rheometer, rotating speed 60rpm, 180 ℃ of blending temperatures; Prepare composite material sheet with 25 tons of compression molding instrument, wherein processing temperature is at 180 ℃, warm up time 12min, hot pressing time 10min, time 8min colds pressing.Also contrast according to the mechanical property result PP base wood-plastic composite material that adds the wood powder that is untreated, tensile strength 53MPa has improved 140%, and flexural strength 54MPa has improved 75%, and modulus in flexure 2300MPa has improved 20%, shock strength 7KJ/m
2Improved 55%.Can find out that by result boiling of wood powder processed and there is obvious synergistic effect in compatilizer, significantly improve the mechanical property of material.
Embodiment 3
Adopt 80 purpose Poplar Powders, jewel bamboo wood powder company limited provides by Linan, Zhejiang; PP, Sinopec Shanghai chemical inc provides, trade mark T300; PP-g-mah, Nanjing moral bar chemical industry company limited provide, percentage of grafting approximately 1%.With electric kettle, wood powder is boiled processing, added wood powder and water than 1: 10 by wood powder and quality, boil 15min after water boiling, stopped heating and suction filtration while hot, the wood powder filter cake is carried out Saunas with vacuum drying oven process 12h, the vacuum tightness of baking oven is at 0.09-0.1MPa.After processing finishes, open the dry wood powder of oven door to constant weight, the then 80 orders processing of sieving.
Wood powder 60phr after processing and the PP-g-mah of PP 40phr and 5phr are added melt blending 15min in the HAAKE rheometer, rotating speed 60rpm, 180 ℃ of blending temperatures; Prepare composite material sheet with 25 tons of compression molding instrument, wherein processing temperature is at 180 ℃, warm up time 12min, hot pressing time 10min, time 8min colds pressing.By national standard test mechanical property, tensile strength is at 20~30MPa, and flexural strength is at 25~35MPa, and modulus in flexure is at 2900~3500MPa, and shock strength is at 2.5~4KJ/m
2, heat-drawn wire can reach more than 120 ℃.