CN102627824B - Method for manufacturing polymerized wood by pre-irradiation grafting - Google Patents
Method for manufacturing polymerized wood by pre-irradiation grafting Download PDFInfo
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- CN102627824B CN102627824B CN201210072787.3A CN201210072787A CN102627824B CN 102627824 B CN102627824 B CN 102627824B CN 201210072787 A CN201210072787 A CN 201210072787A CN 102627824 B CN102627824 B CN 102627824B
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Abstract
The invention discloses a method for manufacturing polymerized wood by pre-irradiation grafting. The method comprises the following steps of 1, mixing straw powder and methyl methacrylate, carrying out kneading of the mixture and carrying out irradiation of the mixture in an inert gas protective atmosphere to obtain a grafted modified woody polymerized material, 2, mixing a thermoplastic resin and acrylic acid, carrying out kneading of the mixture and carrying out irradiation of the mixture in an inert gas protective atmosphere to obtain a grafted modified plasticized polymerized material, and 3, mixing the grafted modified woody polymerized material and the grafted modified plasticized polymerized material, carrying out kneading of the mixture, adding a filling material into the mixture, uniformly mixing and carrying out extrusion molding to obtain the polymerized wood. The method has the advantages of sufficient raw material sources, simple processes, high grafting rate, low use amount of an auxiliary agent, no need of a chemical adhesive, clean and eco-friendly characteristics and low cost. The polymerized wood obtained by the method has the advantages of good mechanical properties, high heat stability, no pollution, corrosion resistance and aging resistance.
Description
Technical field
The invention belongs to nuclear radiation tech Application Areas, be specifically related to a kind of method of pre-irradiation grafting manufacture polymerization wood.
Background technology
Crop stalk is as a kind of by product of agriculture production, output is large, distribute wide, also be important Biological resources, annual approximately 500,000,000-600,000,000 tons of current China crop straw generation according to statistics, it is exactly to make it be processed into another kind of utilizable product by various processing approach unnecessary refuse stalk that agricultural crop straw utilizes technology.For a long time, both at home and abroad the comprehensive utilization of crop stalk is conducted extensive research, obtained many approach for utilizing.
There are four large defects in the wooden recombinant product such as widely used fiberboard, high-density plate, woodwork plate, shaving board in the market: the one, and the consistency of undressed xylon and plastics is poor, and it is not tight that plastics are combined with vegetable fibre, causes material quality to decline; The 2nd, wood effect is undesirable; The 3rd, use in a large number resol as tackiness agent, cause a large amount of release formaldehydes of product, be detrimental to health; To environment, and mechanical property is also poor, and cost is also higher; The 4th, still consume in a large number timber resources, restricted the development space of product, or in technique, technical, qualitatively, also there are some problems in the aspect such as environmental pollution.Really can form scale production, what can consume in a large number straw utilizes approach also few, or economic benefit is not remarkable, and increment is little.Therefore, many local using crop stalk as waste, this is the significant wastage to resource still not, brings about great losses economically, and environment has also been caused to very large pollution.Therefore,, as an important component part in wooden restructuring field, the polymerization of research vegetable fibre and plastics macromolecular material, has special significance to production polymerization wood composite material.
Polymerization wood be with the woody debris such as timber, stalk, shrub branch be main raw material, use initiator initiating chamical reaction, impel wood materials to plastify and regroup, compound after, approach natural wood materials most by plastic working method produced one.The polymerization wood wood materials all the components that has been unique so far utilization, and substantially not discharged waste, not containing the artificial wooden material of the toxic substances such as formaldehyde.But the wood-plastic composite material products of producing in the market, substantially takes chemical assistant to cause wood as reaction initiator and moulds and combine, then extrusion moulding under different processing condition.In the matrix material preparing, all contain certain chemical composition, environment is had to certain pollution, be unfavorable for the requirement of cleaner production.
The patent of invention of notification number CN101186754B discloses a kind of method of utilizing crop straw to produce macromolecule composite wood-plastic material, comprise: crop straw is pulverized and is dried and to obtain straw powder, straw powder is carried out to dip treating, then be dried to obtain modified straw powder, be that other main raw material carries out high-speed mixing and cooling mixing obtains dry mash by modified straw powder and plastics, dry mash is carried out to extruding pelletization, then the material after granulation is extruded qualitative, make macromolecule composite wood-plastic material.The Wood-plastic material that the method makes has good material property, but its complex process, chemical assistant kind reaches kind more than ten, all containing toxic and harmful substance, does not meet the requirement of cleaner production, environmental protection.It is section material synthesized and preparation method thereof that the application for a patent for invention of publication number CN1887967A discloses a kind of stalk, and preparation process comprises: agricultural crop straw is dried to moisture content at 8-15%, is then crushed to 100-300 order; Get in proportion batching, batching is uniformly mixed and is placed in refiner, refining 10-15 minute under 130-170 ℃ of condition; Compound after refining is extruded cooling forming with duplex forcing machine; Wherein, batching comprises agricultural crop straw powder, Plastic Resin, calcium carbonate, brightener.The method technique is simple, does not use chemical binder, but that prepared section bar wood is moulded polymerization effect is bad, and the mechanical property of section bar is still not ideal enough.
Summary of the invention
The invention provides a kind of pre-irradiation grafting and manufacture the method for polymerization wood, technique is simple, and auxiliary dosage is few, clean environment firendly, and the polymerization wood making has good mechanical property and thermostability, pollution-free, corrosion-resistant, ageing-resistant, cost is low.
Pre-irradiation grafting is manufactured a method for polymerization wood, comprising:
(1) straw powder and methyl methacrylate are mixed to refining; After refining completes, be placed under protection of inert gas and carry out radiation treatment, obtain the poly-material of graft modification wood;
(2) thermoplastic resin and vinylformic acid are mixed to refining; After refining completes, be placed under protection of inert gas and carry out radiation treatment, obtain graft modification and mould poly-material;
(3) wooden graft modification poly-material and graft modification are moulded to poly-material mixing, refining; After refining completes, interpolation filler, mixes, and extrusion moulding makes polymerization wood;
Wherein, each raw material consumption accounts for the weight percent of all raw material total amounts and is: straw powder 40-50%, methyl methacrylate 2-3%, thermoplastic resin 30-40%, vinylformic acid 1-2%, filler 10-15%.
Because main component in straw powder is Mierocrystalline cellulose, cellulose surface contains a large amount of hydroxyls and phenolic aldehyde base functional group, makes in molecule and intermolecularly has a hydrogen bond that polarity is very strong, causes straw powder to have the strong polarity on water-absorbent and surface; And thermoplastic resin mostly is apolar substance, there is hydrophobic group, therefore, the interface compatibility between straw powder and thermoplastic resin is very poor, and interfacial adhesion is very poor.By described radiation treatment, can make the functional group of Mierocrystalline cellulose end produce free radical, methyl methacrylate has plural functional group, with the functional groups of Mierocrystalline cellulose end, can realize cellulosic graft modification; Meanwhile, irradiation can make the functional group of thermoplastic resin end produce free radical, and vinylformic acid has plural functional group, with the functional groups of thermoplastic resin end, can realize the graft modification to thermoplastic resin.Through the Mierocrystalline cellulose of graft modification and easier polymerization between the thermoplastic resin of graft modification.
Described straw powder by crop stalk drying, pulverize after obtain.
Described crop stalk can be at least one in grass stalk, barley straw, wheat straw, cotton stalk, rice husk, Pericarppium arachidis hypogaeae, beans tangerine.In order to save cost and comprehensive utilization, described crop stalk can be selected crop straw refuse as far as possible.
The biodiversity content of described straw powder is preferably 12-15%, and while being dried, it is 12-15% that crop stalk is dried to biodiversity content.Moisture content is too high is unfavorable for polymerization, and excess moisture can make material foaming, affects the mechanical property of product.Under this moisture content condition, be conducive to wood most and mould polymerization, and the mechanical property of polymerization wood is better.
The particle diameter of described straw powder is preferably 50-80 order, can effectively reduce the contact area between raw material space length, increase powder each other, and the polymerization making wood compactness is good, density is large, has good mechanical property simultaneously.
Described thermoplastic resin can be polyethylene (PE) or polypropylene (PP).In order to save cost and comprehensive utilization, described thermoplastic resin can be selected waste and old PE or PP plastics.
Described filler can increase the weight of product, and improves product mechanical property.Described filler can be calcium carbonate or talcum powder; Be preferably calcium carbonate; More preferably nanometer grade calcium carbonate.Nanometer grade calcium carbonate has quantum size effect, small-size effect, surface effects and macroscopic quantum effect, is better than conventional material at aspects such as magnetic, catalytic, photo-thermal resistance and fusing points.Because its size is less, can be penetrated in the space that straw powder is combined with thermoplastic resin, tamped density is increased, can make using it as filler that polymerization wood surface light is gorgeous, extensibility is large, tension stress is high, strong, the resistance to bending of anti-tear power, cracking be good, has good strengthening action.
Described thermoplastic resin, methyl methacrylate, vinylformic acid or filler can adopt commercially available civilian or industrial reagent commodity.
In step (1), described refining can make straw powder and methyl methacrylate pre-mixing even, fast grafting while being beneficial to follow-up irradiation.Described refining temperature is preferably 130-150 ℃, and the refining time is preferably 30-40 minute, and refining speed is preferably 700-900 rev/min, and mixing, refining effect to straw powder and methyl methacrylate are best.
In step (2), described refining can make thermoplastic resin and vinylformic acid pre-mixing even, fast grafting while being beneficial to follow-up irradiation.Described refining temperature is preferably 120-140 ℃, and the refining time is preferably 20-30 minute, and refining speed is preferably 700-900 rev/min, best to thermoplastic resin and acrylic acid mixing, refining effect.
In step (3), the wooden poly-material of graft modification and graft modification are moulded after poly-material mixing, and described refining temperature is preferably 150-160 ℃, and the refining time is preferably 35-45 minute, and refining speed is preferably 1100-1300 rev/min.Refining temperature is too small to be unfavorable for that wood is moulded and to mix, and under this refining condition, the poly-material of grafting innovation wood, graft modification is moulded outside poly-stock ground to polymerization effect best.
Add after filler, described mixing can be undertaken by stirring at normal temperatures; Churning time is preferably 10-20 minute, and stirring velocity is preferably 400-600 rev/min.
In extrusion, for the coefficient of friction between minimizing equipment and material, can add lubricant.Described lubricant can be paraffin wax, Viscotrol C or white oil.
While adopting forcing machine to extrude, each section of temperature setting can be: I section: 150～170 ℃; II section: 160～190 ℃: III section: 170～195 ℃: IV section: 180～195 ℃; Machine head port mould section: 180～205 ℃.Under this extrusion condition, can make the good polymerization wood of mechanical property.The actual temp of each section can regulate by the mobility status in forcing machine at any time according to material, crosses when slow and can suitably heighten temperature when Flow of Goods and Materials; In the time that Flow of Goods and Materials is too fast, can suitably reduce temperature, in case material incipient scorch.
In step (1) or (2), described rare gas element can be helium or nitrogen.Oxygen has inhibition to graft reaction, when radiation treatment, if there is air or oxygen in material, can affect the graft effect between raw material, carries out radiation treatment and be more conducive to the graft modification to straw powder or thermoplastic resin under described protection of inert gas.
For the radiation environment of anaerobic is provided, the raw material after refining can being completed is loaded in plastics bag, and inflated with nitrogen secures sack, then carries out described radiation treatment.Described plastics bag is preferably polyethylene plastic bag or polypropylene plastics pocket; More preferably polyethylene plastic bag, polyethylene plastic bag has good radioresistance, is not easy breakage.
Described radiation treatment can be processed or gamma-ray irradiation processing for electron beam irradiation; Be preferably electron beam irradiation processing.The radiation dose of described radiation treatment is preferably 20-30kGy.Because electron beam irradiation energy is high, irradiation dose can interrupt in the short period of time Mierocrystalline cellulose and methyl methacrylate in the time of 20-30kGy, or the molecular linkage on thermoplastic resin and vinylformic acid end correct position, thereby form unsettled free radical, between corresponding free radical, combination forms covalent linkage fast, bonding force is strong, thereby realizes the graft modification to Mierocrystalline cellulose or thermoplastic resin, and percentage of grafting is higher.
Described refining equipment can adopt refiner.
Described radiation treatment equipment can adopt 10Mev rumbatron.
Described extrusion equipment can adopt twin screw extruder.
In the present invention, the structural formula of methyl methacrylate is CH
2c (CH
3) COOCH
3, acrylic acid structural formula is H
2c=CH-CO-OH, all has more than two functional group.The inventive method utilizes ray as initiator, under the electron beam irradiation effect of appropriate dose (20-30kGy), hydrogen atom on the carbon atom being connected with hydroxyl in cellulosic molecule is seized and is produced hydroxyl (OH) free radical, functional group's ionization on methyl methacrylate produces hydrogen (H) free radical, be combined into covalent linkage with the hydroxyl effect in cellulosic molecule, making Mierocrystalline cellulose is nonpolar by polarity transformation; A functional group on vinylformic acid, under effects of ionizing radiation, produces active extremely strong hydroxyl (OH) free radical too, with the CH effect in PP or PE functional group, forms CH
2o conjugated double bond.Under the initiation of certain temperature outside the venue, in methyl methacrylate, hydroxyl radical free radical reacts with acrylic acid hydroperoxyl radical (H) again, has realized the connection of covalent linkage.Thereby realize the connection of chemical bond between cellulose-methyl methacrylate-vinylformic acid-thermoplastic resin.
The present invention is by appropriate irradiation and suitable graft modification agent (methyl methacrylate, vinylformic acid) acting in conjunction, the interfacial energy of wood between moulding reduced, interfacial viscosity strength increase, both easier polymerizations, and do not need to use other chemical binder; Effectively improve the over-all properties of prepared polymerization wood simultaneously.
Compared with prior art, the present invention has following useful technique effect:
(1) sufficient raw, technique is simple, adopts physical refining processes, and percentage of grafting is high; Auxiliary dosage is few, without the tackiness agent that adds any chemosynthesis, only contains straw powder, thermoplastic resin, methyl methacrylate, vinylformic acid and filler in the polymerization wood making, and noresidue is nonpoisonous and tasteless, environmental protection.
(2) raw material adopting can at utmost utilize waste, has both realized the comprehensive utilization of agricultural crop straw dead meal and waste or used plastics, has effectively reduced again production cost.
(3) advantages such as the polymerization wood outward appearance smooth finish that adopts the inventive method to prepare is good, and compactness is good, has good mechanical property and thermostability, and has sound-absorbing, heat insulation, fire prevention, corrosion-resistant, ageing-resistant; Meanwhile, polymerization Muyi processing, can dig, saws or cut a hole, and can be used for ground decoration, flower bed decoration, construction and decoration, the Furniture manufacture on outdoor guardrail, floor, banister and railing, walkway etc. and lives with fields such as woodworks.
Embodiment
Describe the present invention in detail below in conjunction with embodiment, but the present invention is not limited to this.
Embodiment 1
Pre-irradiation grafting is manufactured a method for polymerization wood, comprises the following steps:
(1) harvested crop stalk (rice husk) is dried, until biodiversity content is 12%; Then put into pulverizer, be crushed to 50 orders, obtain straw powder.
(2) straw powder is inserted in refiner, add while stirring methyl methacrylate, in 130 ℃ of refinings 40 minutes, refiner rotating speed was 800 revs/min; After refining completes, pack in PE (polyethylene) plastics bag, 25 kilograms every bag, inflated with nitrogen 10 minutes, secures sack; Mixture after adopting rumbatron to pack carries out electron beam irradiation processing, and radiation dose is 20kGy, obtains the poly-material of graft modification wood.
(3) thermoplastic resin (PP) is inserted in refiner, add while stirring vinylformic acid, in 120 ℃ of refinings 30 minutes, refiner rotating speed was 800 revs/min; After refining completes, pack in PE (polyethylene) plastics bag, 25 kilograms every bag, inflated with nitrogen 10 minutes, secures sack; Mixture after adopting rumbatron to pack carries out electron beam irradiation processing, and radiation dose is 20kGy, obtains graft modification and moulds poly-material.
(4) the poly-material of graft modification wood step (2) being obtained, the graft modification that step (3) obtains are moulded poly-material and are inserted in refiner again, and in 150 ℃ of refinings 40 minutes, refiner rotating speed was 1200 revs/min.
(5) after refining completes, in refiner, add filler (nanometer grade calcium carbonate), stir 15 minutes under normal temperature, stirring velocity is 500 revs/min.
(6) after having stirred, extrude with duplex forcing machine, in extrusion, uninterruptedly add lubricant (paraffin wax) with the coefficient of friction between minimizing equipment and material; Forcing machine is extruded each section of temperature and is arranged as follows: I section: 150～170 ℃; II section: 160～190 ℃: III section: 170～195 ℃: IV section: 180～195 ℃; Machine head port mould section: 180～205 ℃, the mobility status in forcing machine regulates the actual temp of each section at any time according to material, to control suitable material flow.
(7) cooling forming obtains polymerization wood.
Wherein, each raw material consumption accounts for the weight percent of all raw material total amounts and is: straw powder 40%, methyl methacrylate 3%, thermoplastic resin (PP) 40%, vinylformic acid 2%, filler (nanometer grade calcium carbonate) 15%.
Embodiment 2
Pre-irradiation grafting is manufactured a method for polymerization wood, comprises the following steps:
(1) harvested crop stalk (Pericarppium arachidis hypogaeae) is dried, until biodiversity content is 15%; Then put into pulverizer, be crushed to 80 orders, obtain straw powder.
(2) straw powder is inserted in refiner, add while stirring methyl methacrylate, in 150 ℃ of refinings 30 minutes, refiner rotating speed was 800 revs/min; After refining completes, pack in PE (polyethylene) plastics bag, 25 kilograms every bag, inflated with nitrogen 10 minutes, secures sack; Mixture after adopting rumbatron to pack carries out electron beam irradiation processing, and radiation dose is 30kGy, obtains the poly-material of graft modification wood.
(3) thermoplastic resin (PE) is inserted in refiner, add while stirring vinylformic acid, in 140 ℃ of refinings 20 minutes, refiner rotating speed was 800 revs/min; After refining completes, pack in PE (polyethylene) plastics bag, 25 kilograms every bag, inflated with nitrogen 10 minutes, secures sack; Mixture after adopting rumbatron to pack carries out electron beam irradiation processing, and radiation dose is 30kGy, obtains graft modification and moulds poly-material.
(4) the poly-material of graft modification wood step (2) being obtained, the graft modification that step (3) obtains are moulded poly-material and are inserted in refiner again, and in 150 ℃ of refinings 40 minutes, refiner rotating speed was 1200 revs/min.
(5) after refining completes, in refiner, add filler (nanometer grade calcium carbonate), stir 15 minutes under normal temperature, stirring velocity is 500 revs/min.
(6) after having stirred, extrude with duplex forcing machine, in extrusion, uninterruptedly add lubricant (white oil) with the coefficient of friction between minimizing equipment and material; Forcing machine is extruded each section of temperature and is arranged as follows: I section: 150～170 ℃; II section: 160～190 ℃: III section: 170～195 ℃: IV section: 180～195 ℃; Machine head port mould section: 180～205 ℃, the mobility status in forcing machine regulates the actual temp of each section at any time according to material, to control suitable material flow.
(7) cooling forming obtains polymerization wood.
Wherein, each raw material consumption accounts for the weight percent of all raw material total amounts and is: straw powder 50%, methyl methacrylate 2%, thermoplastic resin (PE) 35%, vinylformic acid 1%, filler (nanometer grade calcium carbonate) 12%.
Table 1 shows the composition ingredients by weight per-cent of two embodiment and the mechanical property of polymerization wood thereof of pre-irradiation grafting manufacture polymerization wood.
Table 1
Claims (7)
1. pre-irradiation grafting is manufactured a method for polymerization wood, it is characterized in that, comprising:
(1) straw powder and methyl methacrylate are mixed to refining; After refining completes, be placed under protection of inert gas and carry out radiation treatment, obtain the poly-material of graft modification wood;
(2) thermoplastic resin and vinylformic acid are mixed to refining; After refining completes, be placed under protection of inert gas and carry out radiation treatment, obtain graft modification and mould poly-material;
(3) wooden graft modification poly-material and graft modification are moulded to poly-material mixing, refining; After refining completes, interpolation filler, mixes, and extrusion moulding makes polymerization wood;
Wherein, each raw material consumption accounts for the weight percent of all raw material total amounts and is: straw powder 40-50%, methyl methacrylate 2-3%, thermoplastic resin 30-40%, vinylformic acid 1-2%, filler 10-15%;
Described thermoplastic resin is polyethylene or polypropylene;
In step (1) or (2), described radiation treatment is electron beam irradiation processing;
In step (1) or (2), the radiation dose of described radiation treatment is 20-30kGy.
2. method according to claim 1, is characterized in that, the biodiversity content of described straw powder is 12-15%.
3. method according to claim 1, is characterized in that, the particle diameter of described straw powder is 50-80 order.
4. method according to claim 1, is characterized in that, in step (1), described refining temperature is 130-150 ℃, and the refining time is 30-40 minute.
5. method according to claim 1, is characterized in that, in step (2), described refining temperature is 120-140 ℃, and the refining time is 20-30 minute.
6. method according to claim 1, is characterized in that, in step (3), described refining temperature is 150-160 ℃, and the refining time is 35-45 minute.
7. method according to claim 1, is characterized in that, in step (1) or (2), described rare gas element is helium or nitrogen.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210072787.3A CN102627824B (en) | 2012-03-19 | 2012-03-19 | Method for manufacturing polymerized wood by pre-irradiation grafting |
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| CN201210072787.3A CN102627824B (en) | 2012-03-19 | 2012-03-19 | Method for manufacturing polymerized wood by pre-irradiation grafting |
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| CN102627824B true CN102627824B (en) | 2014-06-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625845A (en) * | 1968-03-08 | 1971-12-07 | Mitsubishi Petrochemical Co | Particulate grafted cellulose-polyolefin compositions |
| GB1287143A (en) * | 1969-01-30 | 1972-08-31 | Arthur Charlesby | Novel crosslinked polymer |
| CN1397596A (en) * | 2002-07-31 | 2003-02-19 | 张发饶 | Process for preparing thermoplastic wood powder |
| CN101754599A (en) * | 2008-12-16 | 2010-06-23 | 金发科技股份有限公司 | Application of injection molding wood plastic composite in producing electric appliance housing |
| CN101747640A (en) * | 2008-12-16 | 2010-06-23 | 金发科技股份有限公司 | Modified plant powder for wood-plastics and preparation method and application thereof |
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2012
- 2012-03-19 CN CN201210072787.3A patent/CN102627824B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625845A (en) * | 1968-03-08 | 1971-12-07 | Mitsubishi Petrochemical Co | Particulate grafted cellulose-polyolefin compositions |
| GB1287143A (en) * | 1969-01-30 | 1972-08-31 | Arthur Charlesby | Novel crosslinked polymer |
| CN1397596A (en) * | 2002-07-31 | 2003-02-19 | 张发饶 | Process for preparing thermoplastic wood powder |
| CN101754599A (en) * | 2008-12-16 | 2010-06-23 | 金发科技股份有限公司 | Application of injection molding wood plastic composite in producing electric appliance housing |
| CN101747640A (en) * | 2008-12-16 | 2010-06-23 | 金发科技股份有限公司 | Modified plant powder for wood-plastics and preparation method and application thereof |
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