CN102627864A - Method for manufacturing polymerized wood by irradiation polymerization - Google Patents
Method for manufacturing polymerized wood by irradiation polymerization Download PDFInfo
- Publication number
- CN102627864A CN102627864A CN2012100731811A CN201210073181A CN102627864A CN 102627864 A CN102627864 A CN 102627864A CN 2012100731811 A CN2012100731811 A CN 2012100731811A CN 201210073181 A CN201210073181 A CN 201210073181A CN 102627864 A CN102627864 A CN 102627864A
- Authority
- CN
- China
- Prior art keywords
- straw powder
- polymerization
- thermoplastic resin
- wood
- straw
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a method for manufacturing polymerized wood by irradiation polymerization. The method comprises the following steps of mixing straw powder, a thermoplastic resin and isopropyl titanate, carrying out kneading of the mixture to obtain a mixed material, carrying out irradiation treatment on the mixed material in an inert gas protective atmosphere, then adding a filling material into the irradiated mixed material, mixing uniformly, and carrying out extrusion molding to obtain the polymerized wood, wherein the polymerized wood comprises: by weight, 40 to 57% of the straw powder, 30 to 40% of the thermoplastic resin, 3 to 6% of isopropyl titanate and 10 to 16% of the filling material. The method has the advantages of sufficient raw material sources, simple processes, low auxiliary agent amount, no need of a chemical adhesive, clean and eco-friendly characteristics and low production 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 polymerization wood is made in a kind of mutual radiation polymerization.
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 wood-based products 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 is not still to the significant wastage of resource; Bring about great losses economically, and environment has also been caused very big pollution.
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 and 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 mutual radiation polymerization 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.
The method of polymerization wood is made in a kind of mutual radiation polymerization, comprising:
(1) straw powder, thermoplastic resin and isopropyl titanate are mixed, rub refining, obtain mixing materials;
(2) under protection of inert gas, mixing materials is carried out radiation treatment;
(3) finish dealing with after, add filler, 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 40-57%, thermoplastic resin 30-40%, isopropyl titanate 3-6%, filler 10-16%.
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 and thermoplastic resin produce radical, isopropyl titanate has plural functional group, mutually combines between the functional group to realize the polymerization of three kinds of materials.
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 10-12%, and when promptly dry, it is 10-12% 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 the polymerization between straw powder and the thermoplastic resin most, and the mechanical property of polymerization wood is better.
The particle diameter of said straw powder is preferably the 40-80 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, isopropyl titanate or filler can adopt commercially available civilian or industrial reagent commodity.
In the step (1), describedly rub refining and can make straw powder, thermoplastic resin and isopropyl titanate pre-mixing even, copolymerization 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 20-30 minute, rubs refining speed and is preferably 700-900 rev/min, to the mixing of raw material, to rub the refining effect best.
In the step (2), described rare gas element can be helium or nitrogen.Oxygen has gathering property of resistance to polyreaction, during radiation treatment, if having air or oxygen in the material, can influence the polymerization effect between the raw material, more helps the polymerization of wood between moulding carrying out radiation treatment under the described protection of inert gas.
For the radiation environment of anaerobic is provided, can mixing materials 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 the molecular linkage on Mierocrystalline cellulose, the terminal correct position of thermoplastic resin in the short period of time when 20-30kGy; Thereby form unsettled radical; The terminal radical of Mierocrystalline cellulose and thermoplastic resin combines to form covalent linkage fast with isopropyl titanate, and bonding force is strong, thereby realizes copolymerization.
In the step (3), behind the interpolation 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.
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 molecular formula of isopropyl titanate is (CH
3CH
3CHO)
4Ti 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 isopropyl titanate produces hydrogen (H) radical, is combined into covalent linkage with hydroxyl effect in the cellulosic molecule; CH effect in another functional group (H) on the isopropyl titanate and PP or the PE functional group forms conjugated double bond.Thereby realized the connection of chemical bond between Mierocrystalline cellulose-isopropyl titanate-thermoplastic resin.
The present invention reduces the interfacial energy of wood between moulding through the irradiation and suitable coupling agents (isopropyl titanate) acting in conjunction of appropriateness, 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; Auxiliary dosage is few, need not to add the tackiness agent of any chemosynthesis, only contains straw powder, thermoplastic resin, isopropyl titanate 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
The method of polymerization wood is made in a kind of mutual radiation polymerization, may further comprise the steps:
(1) harvested crop stalk (barley straw) is dried, until the moisture mass content 10%; Then, the exsiccant stalk is put into kibbler, be crushed to 40 orders, obtain straw powder.
(2) above-mentioned straw powder and thermoplastic resin (PP) are inserted in the refiner, add isopropyl titanate, rub in 130 ℃ and refined 30 minutes, rubbing refining speed is 800 rev/mins, obtains mixing materials.
(3) mixing materials is packed in PE (Vilaterm) plastics bag, 25 kilograms every bag, inflated with nitrogen 30 minutes secures sack; Mixing materials after adopting rumbatron to pack is carried out the electron beam irradiation processing, and radiation dose is 30kGy, obtains the modification by copolymerization mixing materials.
(4) the modification by copolymerization mixing materials is placed refiner, add filler (nanometer grade calcium carbonate), stirred at normal temperatures 15 minutes, stirring velocity is 500 rev/mins.
(5) after stirring is accomplished, extrude, in the extrusion, uninterruptedly add lubricant (Viscotrol C) with the coefficient of friction between minimizing equipment and the material with the duplex forcing machine; Each section temperature 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.
(6) 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%, thermoplastic resin (PP) 40%, isopropyl titanate 4%, filler (nanometer grade calcium carbonate) 16%.
Embodiment 2
The method of polymerization wood is made in a kind of mutual radiation polymerization, may further comprise the steps:
(1) harvested crop stalk (wheat straw) is dried, until the moisture mass content 12%; Then, the exsiccant stalk is put into kibbler, be crushed to 80 orders, obtain straw powder.
(2) above-mentioned straw powder and thermoplastic resin (PE) are inserted in the refiner, add isopropyl titanate, rub in 150 ℃ and refined 20 minutes, rubbing refining speed is 800 rev/mins, obtains mixing materials.
(3) mixing materials is packed in PE (Vilaterm) plastics bag, 25 kilograms every bag, inflated with nitrogen 30 minutes secures sack; Mixing materials after adopting rumbatron to pack is carried out the electron beam irradiation processing, and radiation dose is 20kGy, obtains the modification by copolymerization mixing materials.
(4) the modification by copolymerization mixing materials is placed refiner, add filler (nanometer grade calcium carbonate), stirred at normal temperatures 15 minutes, stirring velocity is 500 rev/mins.
(5) 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.
(6) 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 54%, thermoplastic resin (PE) 30%, isopropyl titanate 6%, filler (nanometer grade calcium carbonate) 10%.
Table 1 shows composition ingredients by weight per-cent and wooden mechanical property of polymerization thereof that two embodiment of polymerization wood are made in the mutual radiation polymerization.
Table 1
Claims (10)
1. wooden method of polymerization is made in a mutual radiation polymerization, it is characterized in that, comprising:
(1) straw powder, thermoplastic resin and isopropyl titanate are mixed, rub refining, obtain mixing materials;
(2) under protection of inert gas, mixing materials is carried out radiation treatment;
(3) finish dealing with after, add filler, 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 40-57%, thermoplastic resin 30-40%, isopropyl titanate 3-6%, filler 10-16%.
2. method according to claim 1 is characterized in that, described straw powder is obtained after drying, pulverizing by crop stalk; Described crop stalk is at least a in grass stalk, barley straw, wheat straw, cotton stalk, rice husk, Pericarppium arachidis hypogaeae, the beans tangerine.
3. method according to claim 1 is characterized in that, the moisture mass content of said straw powder is 10-12%.
4. method according to claim 1 is characterized in that, the particle diameter of said straw powder is the 40-80 order.
5. method according to claim 1 is characterized in that, described thermoplastic resin is Vilaterm or Vestolen PP 7052.
6. method according to claim 1 is characterized in that, described filler is lime carbonate or talcum powder.
7. method according to claim 1 is characterized in that, described rub the refining temperature be 130-150 ℃, rubbing the refining time is 20-30 minute.
8. method according to claim 1 is characterized in that, described rare gas element is helium or nitrogen.
9. method according to claim 1 is characterized in that, described radiation treatment is that electron beam irradiation is handled.
10. method according to claim 1 is characterized in that, the radiation dose of said radiation treatment is 20-30kGy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100731811A CN102627864A (en) | 2012-03-19 | 2012-03-19 | Method for manufacturing polymerized wood by irradiation polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100731811A CN102627864A (en) | 2012-03-19 | 2012-03-19 | Method for manufacturing polymerized wood by irradiation polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102627864A true CN102627864A (en) | 2012-08-08 |
Family
ID=46586268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100731811A Pending CN102627864A (en) | 2012-03-19 | 2012-03-19 | Method for manufacturing polymerized wood by irradiation polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102627864A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410145A (en) * | 2018-03-23 | 2018-08-17 | 河南省科学院同位素研究所有限责任公司 | The method for preparing stalk fibre/PBAT composite materials based on radiation modification |
| CN109097975A (en) * | 2018-08-17 | 2018-12-28 | 长春工业大学 | A kind of inorganic salt modification natural fiber/composite polyolefine material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625845A (en) * | 1968-03-08 | 1971-12-07 | Mitsubishi Petrochemical Co | Particulate grafted cellulose-polyolefin compositions |
| WO1992007022A1 (en) * | 1990-10-23 | 1992-04-30 | Atomic Energy Of Canada Limited | Process for the preparation of cellulosic fibre-reinforced thermoplastic composite materials |
| US5153241A (en) * | 1985-05-29 | 1992-10-06 | Beshay Alphons D | Polymer composites based cellulose-VI |
| CN101775167A (en) * | 2010-01-18 | 2010-07-14 | 河南省科学院同位素研究所有限责任公司 | Environment protective plastic-wood composite material and preparation method thereof |
-
2012
- 2012-03-19 CN CN2012100731811A patent/CN102627864A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625845A (en) * | 1968-03-08 | 1971-12-07 | Mitsubishi Petrochemical Co | Particulate grafted cellulose-polyolefin compositions |
| US5153241A (en) * | 1985-05-29 | 1992-10-06 | Beshay Alphons D | Polymer composites based cellulose-VI |
| WO1992007022A1 (en) * | 1990-10-23 | 1992-04-30 | Atomic Energy Of Canada Limited | Process for the preparation of cellulosic fibre-reinforced thermoplastic composite materials |
| CN101775167A (en) * | 2010-01-18 | 2010-07-14 | 河南省科学院同位素研究所有限责任公司 | Environment protective plastic-wood composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| M.R.ISMAIL,ET AL.: "Mechanical Properties of Rice Straw Fiber-Reinforced Polymer Composites", 《FIBERS AND POLYMERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410145A (en) * | 2018-03-23 | 2018-08-17 | 河南省科学院同位素研究所有限责任公司 | The method for preparing stalk fibre/PBAT composite materials based on radiation modification |
| CN109097975A (en) * | 2018-08-17 | 2018-12-28 | 长春工业大学 | A kind of inorganic salt modification natural fiber/composite polyolefine material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101186754B (en) | Method for producing macromolecule composite wood-plastic material by utilizing crop straw | |
| CN1062803C (en) | Extruded synthetic wood composition and method for making same | |
| CN101747641B (en) | Polyvinyl wood-plastic composite and method for preparing same | |
| CN101880464B (en) | Bamboo-based/thermoplastic plastic nanocomposite material | |
| CN101787167B (en) | High-performance antibiosis wood plastic composite material and preparation method thereof | |
| CN102643503B (en) | Method for manufacturing polymerized wood by irradiation grafting | |
| CN102417738B (en) | Ageing resistant wood plastic composite modified by titanium oxide fiber and lignin and preparation method thereof | |
| CN102108213A (en) | Preparation method of wood-plastic compound material with improved strength | |
| CN103351557A (en) | PVC wood-plastic composite material and machine shaping method thereof | |
| CN101186755B (en) | Method for preparing coconut shell and thermoplastic plastic composite material | |
| CN101870820B (en) | Antibacterial decorative material made by utilizing cotton stalk and preparation method thereof | |
| CN102260386B (en) | Ecological composite material and preparation method thereof | |
| CN101585970B (en) | Polyolefin wood-plastic composite with low rate of water absorption | |
| CN102627864A (en) | Method for manufacturing polymerized wood by irradiation polymerization | |
| CN101245189A (en) | Straw, rice hull fibre base wood-plastic composite material and manufacture method thereof | |
| CN105949807A (en) | Polyvinyl alcohol-based wood-plastic composite and melting processing method thereof | |
| CN102627824B (en) | Method for manufacturing polymerized wood by pre-irradiation grafting | |
| CN109111752A (en) | A kind of preparation method of fungus-resistant bamboo-plastic composite material | |
| CN104945926A (en) | Biomass environment-friendly wood-replacing board | |
| CN101457024B (en) | Method for producing wood-plastic composite material and produced wood-plastic composite material | |
| CN103881283A (en) | Method for improving thermal degradation capacity of maleic anhydride grafted polypropylene plastic | |
| CN102604407B (en) | Method for manufacturing section by performing co-radiation polymerization | |
| CN102604406A (en) | Method for manufacturing section bar by means of irradiation grafting | |
| CN101380184A (en) | Clothes stand produced by wood-plastics composite material | |
| CN107118458A (en) | A kind of non-foamed PVC bases superelevation filling biomass fiber composite and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120808 |