CN102627824A - 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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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 the nuclear radiation tech Application Areas, be specifically related to the method that a kind of pre-irradiation grafting is made polymerization wood.
Background technology
Crop stalk is as a kind of by product of agriculture prodn; Output is big; It is wide to distribute; Also be important Biological resources, annual about 500,000,000-600,000,000 tons of present according to statistics China crop straw generation, agricultural crop straw utilization technology makes unnecessary refuse stalk it be processed into another kind of utilizable product through various processing approach exactly.For a long time, extensive studies has been carried out in the comprehensive utilization of crop stalk both at home and abroad, obtained many approach that supply to utilize.
There are four big defectives in wooden recombinant product such as widely used in the market wad, high-density plate, woodwork plate, shaving board: the one, and the consistency of undressed xylon and plastics is poor, and it is not tight that plastics combine with vegetable fibre, causes material quality to descend; The 2nd, wood effect is undesirable; The 3rd, use resol as tackiness agent in a large number, cause a large amount of release formaldehydes of product, be detrimental to health; Environment is polluted, and mechanical property is also relatively poor, cost is also higher; The 4th, mass consumption timber resources has still restricted the development space of product, or on technology, technical, qualitatively, also there are some problems in aspect such as environmental pollution.Really can form scale prodn, can mass consumption straw utilize approach and few, or economic benefit is not remarkable, increment is little.Therefore, many local crop stalk as waste, this still to the significant wastage of resource, does not bring about great losses economically, and environment has also been caused very big pollution.Therefore, as an important component part in wooden reorganization field, the polymerization of research vegetable fibre and plastics macromolecular material has special significance to production polymerization wood composite material.
Polymerization wood is to use woody debris such as timber, stalk, shrub branch to be main raw material, uses the initiator initiating chamical reaction, impel wood materials plasticizing and regroup, compound after, produced a kind of with plastic working method near natural wood materials.The polymerization wood wood materials all the components that has been unique so far utilization, and basically not discharged waste, do not contain the artificial wooden material of toxic substances such as formaldehyde.But the wood plastic composite product of producing is in the market taked chemical assistant to cause wood as reaction initiator basically and is moulded and combine extrusion moulding under different technological conditions again.All contain certain chemical ingredients in the matrix material for preparing, environment is had 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 the dry straw powder that gets, straw powder is carried out dip treating, the dry then modified straw powder that gets; With modified straw powder and plastics is that other main raw material carries out mixed at high speed and cooling mixing gets dry mash; Dry mash is carried out extruding pelletization, again the material after the granulation is extruded qualitatively, make macromolecule composite wood-plastic material.The Wood-plastic material that this method makes has material property preferably, but its complex process, the chemical assistant kind reaches kind more than ten, all contains poisonous harmful chemical, does not meet cleaner production, environmental protection requirement.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 crushed to the 100-300 order then; Get batching in proportion, batching is mixed be placed in the refiner, under 130-170 ℃ of condition, rub refining 10-15 minute; The compound of rubbing after the refining is extruded cooling forming with the duplex forcing machine; Wherein, batching comprises agricultural crop straw powder, Plastic Resin, lime carbonate, brightener.This method technology 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 make the method for polymerization wood, technology is simple, and auxiliary dosage is few, clean environment firendly, and the polymerization wood that makes has good mechanical performance and thermostability, and is pollution-free, corrosion-resistant, ageing-resistant, cost is low.
A kind of pre-irradiation grafting is made the method for polymerization wood, comprising:
(1) straw powder and TEB 3K are mixed, rub refining; After rubbing the refining completion, place and carry out radiation treatment under the protection of inert gas, obtain graft modification wood and gather material;
(2) thermoplastic resin and vinylformic acid are mixed, rub refining; Rub after refining accomplishes, place and carry out radiation treatment under the protection of inert gas, obtain graft modification and mould and gather material;
(3) graft modification wood is gathered material and mould with graft modification and gather material mixing, rub refining; Rub and add filler after refining is accomplished, mixing, 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%, TEB 3K 2-3%, thermoplastic resin 30-40%, vinylformic acid 1-2%, filler 10-15%.
Because staple is a Mierocrystalline cellulose in the straw powder, cellulose surface contains a large amount of hydroxyls and phenolic aldehyde base functional group, makes intramolecularly and intermolecular have the very strong hydrogen bond of polarity, causes the straw powder to have water-absorbent and surperficial strong polarity; And mostly thermoplastic resin is apolar substance, has hydrophobic group, and therefore, the interface compatibility between straw powder and thermoplastic resin is very poor, and interfacial adhesion is very poor.Through described radiation treatment, can make the terminal functional group of Mierocrystalline cellulose produce radical, TEB 3K has plural functional group, with the terminal functional groups of Mierocrystalline cellulose, can realize cellulosic graft modification; Simultaneously, irradiation can make the terminal functional group of thermoplastic resin produce radical, and vinylformic acid has plural functional group, with the terminal functional groups of thermoplastic resin, can realize the graft modification to thermoplastic resin.Through the Mierocrystalline cellulose of graft modification and polymerization more easily between the thermoplastic resin of graft modification.
Described straw powder is obtained after drying, pulverizing by crop stalk.
Described crop stalk can be in grass stalk, barley straw, wheat straw, cotton stalk, rice husk, Pericarppium arachidis hypogaeae, the beans tangerine at least a.In order to save cost and comprehensive utilization, said crop stalk can be selected crop straw refuse for use as far as possible.
The moisture mass content of said straw powder is preferably 12-15%, and when promptly dry, it is 12-15% that crop stalk is dried to the moisture mass content.Moisture content is too high to be unfavorable for polymerization, and excess moisture can make material foaming, influences the mechanical property of product.Under this moisture content condition, help wood most and mould polymerization, and the mechanical property of polymerization wood is better.
The particle diameter of said straw powder is preferably the 50-80 order, can reduce each other space length of raw material effectively, increase the contact area between the powder, and the polymerization that makes wood compactness is good, density is big, has the good mechanical performance simultaneously.
Described thermoplastic resin can be Vilaterm (PE) or Vestolen PP 7052 (PP).In order to save cost and comprehensive utilization, said thermoplastic resin can be selected waste and old PE or PP plastics for use.
Described filler can increase the weight of product, and improves the product mechanical property.Described filler can be lime carbonate or talcum powder; Be preferably lime carbonate; Nanometer grade calcium carbonate more preferably.Nanometer grade calcium carbonate has quantum size effect, small-size effect, surface effects and macroscopic quantum effect, is superior to conventional material at aspects such as magnetic, catalytic, photo-thermal resistance and fusing points.Because its size is less; Can be penetrated in straw powder and the thermoplastic resin bonded space; Tamped density is increased, with its as filler can make that polymerization wood surface light is gorgeous, extensibility is big, tension stress is high, strong, the anti-bending of anti-tear power, cracking be good, has strengthening action preferably.
Described thermoplastic resin, TEB 3K, vinylformic acid or filler can adopt commercially available civilian or industrial reagent commodity.
In the step (1), describedly rub refining and can make straw powder and TEB 3K pre-mixing even, grafting fast when being beneficial to follow-up irradiation.The described refining temperature of rubbing is preferably 130-150 ℃, rubs the refining time to be preferably 30-40 minute, rubs refining speed and is preferably 700-900 rev/min, to the mixing of straw powder and TEB 3K, rub that to refine effect best.
In the step (2), describedly rub refining and can make thermoplastic resin and vinylformic acid pre-mixing even, grafting fast when being beneficial to follow-up irradiation.The described refining temperature of rubbing is preferably 120-140 ℃, rubs the refining time to be preferably 20-30 minute, rubs refining speed and is preferably 700-900 rev/min, to thermoplastic resin and acrylic acid mixing, to rub the refining effect best.
In the step (3), graft modification wood gather material and graft modification mould gather material and mix after, described rubbing refined temperature and is preferably 150-160 ℃, rubs the refining time to be preferably 35-45 minute, rubs refining speed and is preferably 1100-1300 rev/min.Rub that the refining temperature is too small to be unfavorable for that wood is moulded and to mix, this is rubbed under the refining condition and the grafting innovation wood to be gathered material, graft modification moulds that to gather outside the stock ground polymerization effect best.
After adding filler, described mixing can carry out through stirring at normal temperatures; Churning time is preferably 10-20 minute, and stirring velocity is preferably 400-600 rev/min.
In the extrusion,, can add lubricant for the coefficient of friction between minimizing equipment and the material.Described lubricant can be paraffin wax, Viscotrol C or white oil.
When adopting forcing machine to extrude, each section temperature is provided with and 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 mechanical property better polymerization wood.The actual temp of each section can be regulated according to the mobility status of material in forcing machine at any time, crosses when Flow of Goods and Materials and can suitably heighten temperature when slow; When Flow of Goods and Materials is too fast, can suitably reduce temperature, in case the material incipient scorch.
In step (1) or (2), described rare gas element can be helium or nitrogen.Oxygen has gathering property of resistance to graft reaction, during radiation treatment, if having air or oxygen in the material, can influence the graft effect between the raw material, under described protection of inert gas, carries out radiation treatment and more helps the graft modification to straw powder or thermoplastic resin.
For the radiation environment of anaerobic is provided, can the raw material of rubbing after refining is accomplished be loaded in the plastics bag, inflated with nitrogen secures sack, carries out described radiation treatment again.Described plastics bag is preferably polyethylene plastic bag or polypropylene plastics pocket; Polyethylene plastic bag more preferably, polyethylene plastic bag has radioresistance preferably, is not easy breakage.
Described radiation treatment can be handled or the gamma-ray irradiation processing for electron beam irradiation; Being preferably electron beam irradiation handles.The radiation dose of said radiation treatment is preferably 20-30kGy.Because the electron beam irradiation energy is high; Irradiation dose can interrupt Mierocrystalline cellulose and TEB 3K in the short period of time when 20-30kGy, the perhaps molecular linkage on the terminal correct position of thermoplastic resin and vinylformic acid, thus form unsettled radical; Combine to form covalent linkage between the corresponding radical fast; Bonding force is strong, thereby realizes the graft modification to Mierocrystalline cellulose or thermoplastic resin, and percentage of grafting is higher.
The said refining equipment of rubbing can adopt refiner.
Said radiation treatment equipment can adopt the 10Mev rumbatron.
Said extrusion equipment can adopt twin screw extruder.
Among the present invention, the structural formula of TEB 3K is CH
2C (CH
3) COOCH
3, acrylic acid structural formula is H
2C=CH-CO-OH all has two above functional groups.The inventive method utilizes ray as initiator; Under the electron beam irradiation effect of appropriate dose (20-30kGy); In the cellulosic molecule with carbon atom that hydroxyl links to each other on Wasserstoffatoms seized and produced hydroxyl (OH) radical; A functional group ionization on the TEB 3K produces hydrogen (H) radical, is combined into covalent linkage with hydroxyl effect in the cellulosic molecule, and making Mierocrystalline cellulose is nonpolar by polarity transformation; A functional group on the vinylformic acid produces active extremely strong hydroxyl (OH) radical too under effects of ionizing radiation, with the CH effect in PP or the PE functional group, form CH
2The O conjugated double bond.Under the initiation of certain temperature outside the venue, hydroxyl radical free radical (H) reacts, has realized the connection of covalent linkage with acrylic acid hydroperoxyl radical once more in the TEB 3K.Thereby realize the connection of chemical bond between cellulose-methyl methacrylate-vinylformic acid-thermoplastic resin.
The present invention is through irradiation and suitable graft modification agent (TEB 3K, the vinylformic acid) acting in conjunction of appropriateness, and the interfacial energy of wood between moulding reduced, and interfacial viscosity intensity increases, both polymerizations more easily, and need not use other chemical binder; Effectively improved simultaneously the over-all properties of prepared polymerization wood.
Compared with prior art, the present invention has following beneficial technical effects:
(1) sufficient raw, technology is simple, adopts physical refining processes, and percentage of grafting is high; Auxiliary dosage is few, need not to add the tackiness agent of any chemosynthesis, only contains straw powder, thermoplastic resin, TEB 3K, vinylformic acid and filler in the polymerization wood that makes, and noresidue is nonpoisonous and tasteless, environmental protection.
(2) raw material that adopts can at utmost utilize waste, has both realized agricultural crop straw dead meal and comprehensive utilization of waste plastics, has reduced production cost again effectively.
Advantages such as the polymerization wood outward appearance smooth finish that (3) adopts the inventive method to prepare is good, and compactness is good, has good mechanical performance and thermostability, and has sound-absorbing, heat insulation, fire prevention, corrosion-resistant, and is ageing-resistant; Simultaneously, polymerization Muyi processing can be dug, saws or cut a hole, and the ground decoration, flower bed decoration, construction and decoration, furniture manufacturing and the life that can be used for outdoor guardrail, floor, banister and railing, walkway etc. are with fields such as woodworks.
Embodiment
Specify the present invention below in conjunction with embodiment, but the present invention is not limited to this.
Embodiment 1
A kind of pre-irradiation grafting is made the method for polymerization wood, may further comprise the steps:
(1) harvested crop stalk (rice husk) is dried, until the moisture mass content 12%; Put into kibbler then, be crushed to 50 orders, obtain straw powder.
(2) the straw powder is inserted in the refiner, add TEB 3K while stirring, rub in 130 ℃ and refined 40 minutes, the refiner rotating speed is 800 rev/mins; After rubbing the refining completion, in the PE that packs into (Vilaterm) plastics bag, 25 kilograms every bag, inflated with nitrogen 10 minutes secures sack; Mixture after adopting rumbatron to pack carries out electron beam irradiation to be handled, and radiation dose is 20kGy, obtains graft modification wood and gathers material.
(3) thermoplastic resin (PP) is inserted in the refiner, add vinylformic acid while stirring, rub in 120 ℃ and refined 30 minutes, the refiner rotating speed is 800 rev/mins; After rubbing the refining completion, in the PE that packs into (Vilaterm) plastics bag, 25 kilograms every bag, inflated with nitrogen 10 minutes secures sack; Mixture after adopting rumbatron to pack carries out electron beam irradiation to be handled, and radiation dose is 20kGy, obtains graft modification and moulds and gather material.
(4) the graft modification wood that step (2) is obtained gathers graft modification that material, step (3) obtain to be moulded and gathers material and insert in the refiner again, rubs refining 40 minutes in 150 ℃, and the refiner rotating speed is 1200 rev/mins.
(5) rub after refining accomplishes, in refiner, add filler (nanometer grade calcium carbonate), stirred 15 minutes down in normal temperature, stirring velocity is 500 rev/mins.
(6) after stirring is accomplished, extrude, in the extrusion, uninterruptedly add lubricant (paraffin wax) with the coefficient of friction between minimizing equipment and the material with the duplex forcing machine; Forcing machine is extruded each section temperature and is provided with as follows: the I section: 150～170 ℃; II section: 160～190 ℃: III section: 170～195 ℃: IV section: 180～195 ℃; The machine head port mould section: 180～205 ℃, the actual temp of each section is regulated according to the mobility status of material in forcing machine at any time, 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%, TEB 3K 3%, thermoplastic resin (PP) 40%, vinylformic acid 2%, filler (nanometer grade calcium carbonate) 15%.
Embodiment 2
A kind of pre-irradiation grafting is made the method for polymerization wood, may further comprise the steps:
(1) harvested crop stalk (Pericarppium arachidis hypogaeae) is dried, until the moisture mass content 15%; Put into kibbler then, be crushed to 80 orders, obtain straw powder.
(2) the straw powder is inserted in the refiner, add TEB 3K while stirring, rub in 150 ℃ and refined 30 minutes, the refiner rotating speed is 800 rev/mins; After rubbing the refining completion, in the PE that packs into (Vilaterm) plastics bag, 25 kilograms every bag, inflated with nitrogen 10 minutes secures sack; Mixture after adopting rumbatron to pack carries out electron beam irradiation to be handled, and radiation dose is 30kGy, obtains graft modification wood and gathers material.
(3) thermoplastic resin (PE) is inserted in the refiner, add vinylformic acid while stirring, rub in 140 ℃ and refined 20 minutes, the refiner rotating speed is 800 rev/mins; After rubbing the refining completion, in the PE that packs into (Vilaterm) plastics bag, 25 kilograms every bag, inflated with nitrogen 10 minutes secures sack; Mixture after adopting rumbatron to pack carries out electron beam irradiation to be handled, and radiation dose is 30kGy, obtains graft modification and moulds and gather material.
(4) the graft modification wood that step (2) is obtained gathers graft modification that material, step (3) obtain to be moulded and gathers material and insert in the refiner again, rubs refining 40 minutes in 150 ℃, and the refiner rotating speed is 1200 rev/mins.
(5) rub after refining accomplishes, in refiner, add filler (nanometer grade calcium carbonate), stirred 15 minutes down in normal temperature, stirring velocity is 500 rev/mins.
(6) after stirring is accomplished, extrude, in the extrusion, uninterruptedly add lubricant (white oil) with the coefficient of friction between minimizing equipment and the material with the duplex forcing machine; Forcing machine is extruded each section temperature and is provided with as follows: the I section: 150～170 ℃; II section: 160～190 ℃: III section: 170～195 ℃: IV section: 180～195 ℃; The machine head port mould section: 180～205 ℃, the actual temp of each section is regulated according to the mobility status of material in forcing machine at any time, 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%, TEB 3K 2%, thermoplastic resin (PE) 35%, vinylformic acid 1%, filler (nanometer grade calcium carbonate) 12%.
Table 1 shows composition ingredients by weight per-cent and wooden mechanical property of polymerization thereof that pre-irradiation grafting is made two embodiment of polymerization wood.
Table 1
Claims (10)
1. a pre-irradiation grafting is made wooden method of polymerization, it is characterized in that, comprising:
(1) straw powder and TEB 3K are mixed, rub refining; After rubbing the refining completion, place and carry out radiation treatment under the protection of inert gas, obtain graft modification wood and gather material;
(2) thermoplastic resin and vinylformic acid are mixed, rub refining; Rub after refining accomplishes, place and carry out radiation treatment under the protection of inert gas, obtain graft modification and mould and gather material;
(3) graft modification wood is gathered material and mould with graft modification and gather material mixing, rub refining; Rub and add filler after refining is accomplished, mixing, 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%, TEB 3K 2-3%, thermoplastic resin 30-40%, vinylformic acid 1-2%, filler 10-15%.
2. method according to claim 1 is characterized in that, the moisture mass content of said straw powder is 12-15%.
3. method according to claim 1 is characterized in that, the particle diameter of said straw powder is the 50-80 order.
4. method according to claim 1 is characterized in that, described thermoplastic resin is Vilaterm or Vestolen PP 7052.
5. method according to claim 1 is characterized in that, in the step (1), described rub the refining temperature be 130-150 ℃, rubbing the refining time is 30-40 minute.
6. method according to claim 1 is characterized in that, in the step (2), described rub the refining temperature be 120-140 ℃, rubbing the refining time is 20-30 minute.
7. method according to claim 1 is characterized in that, in the step (3), described rub the refining temperature be 150-160 ℃, rubbing the refining time is 35-45 minute.
8. method according to claim 1 is characterized in that, in step (1) or (2), described rare gas element is helium or nitrogen.
9. method according to claim 1 is characterized in that, in step (1) or (2), described radiation treatment is that electron beam irradiation is handled.
10. method according to claim 1 is characterized in that, in step (1) or (2), the radiation dose of said radiation treatment is 20-30kGy.
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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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548563A (en) * | 2020-06-18 | 2020-08-18 | 黑龙江省科学院技术物理研究所 | Lignin reinforced polypropylene composite material and preparation method thereof |
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| 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 |
| 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 |
| 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 |
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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 |
| 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 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111548563A (en) * | 2020-06-18 | 2020-08-18 | 黑龙江省科学院技术物理研究所 | Lignin reinforced polypropylene composite material and preparation method thereof |
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