CN101302349A - Maleic anhydride grafted polypropylene wood-plastic composite material and preparation thereof - Google Patents
Maleic anhydride grafted polypropylene wood-plastic composite material and preparation thereof Download PDFInfo
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- CN101302349A CN101302349A CNA2008100603198A CN200810060319A CN101302349A CN 101302349 A CN101302349 A CN 101302349A CN A2008100603198 A CNA2008100603198 A CN A2008100603198A CN 200810060319 A CN200810060319 A CN 200810060319A CN 101302349 A CN101302349 A CN 101302349A
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- maleic anhydride
- anhydride graft
- plastic composite
- wood
- waste
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
The invention relates to a polyolefin-g-MAH wood-plastic composite material and a method for preparing the same. The invention aims to solve the technical problems that: the content of plant fiber in the wood-plastic composite material is increased when the strength of the wood-plastic composite material is increased, thereby improving the wood texture of the appearance of the wood-plastic composite material. The invention is characterized in that: the compositions by weight portion of the composite material are: 100 portions of plant fiber powder, polyolefin-g-MAH and supplementary plastics, wherein the plant fiber powder accounts for 60 to 85 portions of the mixture, the balance being polyolefin-g-MAH and supplementary plastics, wherein, the weight of the polyolefin-g-MAH accounts for 40 to 100 percent ( 70 to 100 percent preferably) of the balance.
Description
Technical field
The present invention relates to wood plastic composite and preparation method thereof, specifically be a kind of be the outward appearance woodiness touch of main raw material preparation and the color utmost point as wood plastic composite of natural timber and preparation method thereof with plant fiber powder and maleic anhydride graft polyolefine.
Background technology
Wood plastic composite is to be main raw material with thermoplastics and plant fiber powder, extrudes (or compacting, injection moulding) moulding through high temperature, and the section bar of making, sheet material or other goods mainly are the substitutes as timber.
The used thermoplastics of preparation wood plastic composite is mainly the thermoplasticity waste or used plastics, and used plant fibres powder is mainly agriculture and forestry organic waste material, as wood powder, bamboo powder, chaff powder, agricultural crop straw powder etc.Therefore, the development of wood plastic composite helps the comprehensive utilization of agriculture and forestry organic waste material, help administering " white pollution " that waste or used plastics causes, help alleviating the pressure that is becoming tight timber day and reduce Deforestation, this has crucial meaning for resource circulation utilization with building a conservation-minded society.
Wood plastic composite can be sawed, can dig, can follow closely as timber; Some performance of wood plastic composite is better than timber, as: the distortion that do not absorb water, do not damage by worms, corrosion-resistant, can 100% recycling or the like as thermoplastics, be a kind of green material.
Because wood plastic composite mainly is the substitute as timber, so people always wish its outward appearance extraordinary image timber.But the common wood-plastic composite that prior art is produced is because vegetable fibre content is lower, plastic content is higher, thereby its outward appearance woodiness touch is not strong.The major cause that the vegetable fibre powder content is difficult to improve is because plant fiber powder is the polar hydroaropic substance, and plastics are nonpolar lipophilicity substance, and both consistencies are very poor.
Prior art mainly is to improve consistency between the interface of plant fiber powder and plastics by add a small amount of coupling agent in prescription.Coupling agent commonly used has phthalate ester coupling agent, silane coupling agent, aluminate coupling agent, maleic anhydride grafted polyethylene (MAH-g-PE), maleic anhydride inoculated polypropylene (MAH-g-PP) etc.
But, the composition complexity of vegetable fibre, contain moisture content and various organism small molecules, and the Mierocrystalline cellulose in its major ingredient, hemicellulose, xylogen exist degraded, phenomenon such as softening in the high temperature process process, the result causes the effect of above-mentioned coupling agent to be adversely affected.For example: the effect on coupling agent and vegetable fibre surface is subjected to the influence of moisture content quite big, and the contained moisture content of vegetable fibre always is difficult to remove fully in the actual production, otherwise easily causes variable color or charing; And for example: even the hydroxyl on coupling agent and plant fiber powder surface has formed ester bond, but because vegetable fibre has the part degraded to take place in the hot briquetting process, the possibility of result can make the part that acts as ester bond break away from Mierocrystalline cellulose or the macromolecular main body of hemicellulose; Or the like.
For above-mentioned reasons, vegetable fibre content is lower in the PE of general extrusion moulding or the PP wood plastic composite; If increase substantially its vegetable fibre content, the intensity of wood plastic composite is obviously reduced, water-intake rate significantly raises.Can make the outward appearance woodiness touch of wood plastic composite product relatively poor and vegetable fibre content is low.
Summary of the invention
The technical problem to be solved in the present invention is when improving wood plastic composite intensity, improves the outward appearance woodiness touch of wood plastic composite by significantly improving the content of vegetable fibre in the wood plastic composite.
The description of wood plastic composite of the present invention:
In order to guarantee in significantly improving wood plastic composite in the vegetable fibre content, also require to improve the intensity of wood plastic composite, reduce its water-intake rate, raw material of the present invention does not adopt a small amount of coupling agent of adding to solve the consistency of vegetable fibre and plastics, but sets about solving compatibility problem from following two aspects:
(1) with waste and old PE in the raw material or the whole or most of modified by maleic acid anhydride graft of using of waste PP, to improve the polarity of plastics;
(2) select for use lubricant that plant fiber powder is carried out surface treatment, the surface polarity of vegetable fibre is reduced with the effect of dispersion plant fiber powder.
By the measure of above two aspects, the polarity difference of plastics and vegetable fibre is reduced, thereby the consistency between them is increased, and do not need to add in addition coupling agent.Adopt the advantage of above-mentioned compatible technique to be: the plant fiber powder consistency after maleic anhydride graft polyolefine and the processing is good, do not need to add in addition coupling agent, and can be when increasing the vegetable fibre powder content, wood plastic composite intensity height, water-intake rate that maintenance makes are low.
The maleic anhydride graft polyolefin wood-plastic composite of technique scheme is characterized in that having following raw material:
Plant fiber powder, maleic anhydride graft polyolefine and the auxilliary weight that adds plastics are 100 parts, wherein plant fiber powder is 60～85 parts (being preferably 70～80 parts), surplus for the maleic anhydride graft polyolefine adds plastics with auxilliary, wherein maleic anhydride graft polyolefine weight accounts for 40～100% (being preferably 70～100%).Promptly in raw material, can all use the maleic anhydride graft polyolefine with plant fiber powder mixes mutually, as required also can be partly with the maleic anhydride graft polyolefine, partly then add plastics with assisting.Described auxilliary to add plastics can be virgin material, and in order to reduce production costs, preferred waste or used plastics is as waste and old ABS, waste and old EVA, waste and old POE, waste and old EPDM, waste and old SBS, waste and old CPE etc.; More preferably waste and old PE and/or waste PP.
Weight of additive is 2～6 parts, and wherein lubricant is 1.5～3 parts, and stablizer is 0.5～1 part, and surplus is tinting material.
Specifically, described plant fiber powder is selected from one or more the mixture of arbitrary proportion in wood powder, bamboo powder, chaff powder, agricultural crop straw powder, the non-crop plants fiber powder;
Described maleic anhydride graft polyolefine is selected from the arbitrary proportion mixture of maleic anhydride graft PE (MAH-g-PE), maleic anhydride graft PP (MAH-g-PE) or two kinds of graftss;
Described lubricant is selected from one or more the mixture in stearic acid, methyl stearate, butyl stearate, stearic amide, Palmiticacid acid amides, amine hydroxybenzene, ethylene bis stearamide, calcium stearate, Zinic stearas, lead laurate, whiteruss, solid paraffin, polyethylene wax, the oxidized polyethlene wax;
Described tinting material is selected from one or more the mixture in cadmium pigment, iron pigment, chromate pigments, the cobalt series pigments, can also add a small amount of carbon black again.This colorize method and this patent prescription and process matching can make and anticorrosion wooden color and the very alike wood plastic composite of outward appearance, and artificial wood effect is good when being used for substituting anticorrosion wood and being used for outdoor garden landscape and building.
Described stablizer comprises photostabilizer and oxidation inhibitor, and photostabilizer is selected from UV-531, UV-1084, UV-774, and oxidation inhibitor is selected from BHT, 1010, DLTP, 330, SP.
The contriver discovers, under the constant condition of the total amount that keeps graft polyolefin and PE (or/and PP), if increase MAH-g-PE (or MAH-g-PP) in the raw material gradually, reduces PE (or PP) simultaneously,
Then under proportioning raw materials of the present invention and preparation method's condition, along with the increase of MAH-g-PE (or MAH-g-PP) content, the intensity of the wood plastic composite that makes, modulus all constantly raise, and water-intake rate reduces, and typical experimental results sees Table 1.
By table 1 as seen, when MAH-g-PE replacing whole PE, the intensity of material is far above common wood-plastic composite, and unlike many reports, along with the increase of MAH-g-PE, the intensity of wood plastic composite raise before this, then reduces, and bulk strength raises few.This is obviously relevant with proportioning raw materials of the present invention and preparation method's characteristics.
Table 1: the relation of the intensity of wood plastic composite and grafting PE consumption
| The prescription number | Wood powder | Lime carbonate | Waste and old PE/ part | Grafting PE/ part | Tensile strength/MPa | Curved allusion quotation intensity/MPa | Shock strength/(kJ/m2) | Modulus in flexure/MPa |
| 0# | 70 | 2 | 28 | 0 | 12.5 | 30 | 3.9 | 2066 |
| 1# | 70 | 2 | 25 | 3 | 15.7 | 36.4 | 6.8 | 3100 |
| 2# | 70 | 2 | 24 | 4 | 17.3 | 40.0 | 7.2 | 3653 |
| 3# | 70 | 2 | 21 | 7 | 21.2 | 48.7 | 8.7 | 3677 |
| 4# | 70 | 2 | 18 | 10 | 27.1 | 52.7 | 10.5 | 3865 |
| 5# | 70 | 2 | 13 | 15 | 33.7 | 54.3 | 13.4 | 4232 |
| 6# | 70 | 2 | 8 | 20 | 36.8 | 60.8 | 13.8 | 4227 |
| 7# | 70 | 2 | 4 | 24 | 37.2 | 63.4 | 14.5 | 4339 |
| 8# | 70 | 2 | 0 | 28 | 40.4 | 66.5 | 15.7 | 5013 |
Similarly studies show that in a large number with table 1, when macromolecular material all or most of when substituting with MAH-g-PE or MAH-g-PP, even vegetable fibre content increases substantially, the wood plastic composite that makes with proportioning raw materials of the present invention and preparation method still has higher intensity and lower water-intake rate.
Maleic anhydride graft polyolefine MAH-g-PE and MAH-g-PP can select for use new PE material and new PP to expect to prepare; In order to reduce production costs and to help environmental protection, preferentially select the maleic anhydride graft PE and the maleic anhydride graft PP that make by waste and old PE and waste PP and maleic anhydride graft reaction for use.
Preparation method's of the present invention description:
Press feed proportioning, plant fiber powder is carried out drying (air-flow rotary flow desiccator commonly used), dried plant fiber powder is mixed in high-speed mixer with other raw material, plastify granulation with the cocurrent and parallel twin screw extruder again and get the wooden grain of moulding, use the conical double screw extruder extrusion moulding then, carry out surface finish at last and handle; Described grinding process is to adopt mechanical means, forcing machine is extruded the ganoid wood plastic composite surface finish that makes fall skim, makes its surface have the lines that is similar to natural timber.
As preferably, when the cocurrent and parallel twin screw extruder carried out the heating plasticizing granulation, head section was not provided with pellet device, but screw head is exposed, and material is directly extruded, and extrudate is delivered to cyclonic separator with fluidized and is cooled off, and remove moisture content and volatile matter, pulverizing makes wood and moulds grain then.
Advantages such as product of the present invention has vegetable fibre powder content height, and its woodiness touch and artificial wood effect are good, and be with low cost; Advantages such as preparation method of the present invention has can adapt to the very high wood plastic composite preparation of vegetable fibre powder content, and mixed effect and plasticizing effect are good.
Embodiment
The present invention is described in further detail by following examples, but enforcement of the present invention is not limited to these embodiment.
Preparation method's of the present invention specific descriptions.
1, with air-flow cyclone drying machine or other drying plant plant fiber powder is dried to water content and is lower than 2%;
2, waste and old PE or waste PP are mixed with maleic anhydride, initiator add the cocurrent and parallel twin screw extruder and carry out reactivity and extrude, make maleic anhydride graft PE or maleic anhydride graft PP;
3, by the prescription requirement plant fiber powder, MAH-g-PE and/or MAH-g-PE, lubricant, tinting material, stablizer are added etc. to go into high-speed mixer and mix;
4, compound is added the cocurrent and parallel twin screw extruder and plastify granulation.In order to adapt to the very high prescription plasticizing granulation of vegetable fibre content of the present invention, when carrying out the heating plasticizing granulation with the cocurrent and parallel twin screw extruder, head section is not provided with pellet device, material is directly extruded, extrudate is delivered to cyclonic separator with fluidized and is cooled off, and remove moisture content and volatile matter, pulverize then make the wooden grain of moulding;
5, will pulverize pellet adding conical double screw extruder and extrude, make ganoid wood plastic composite;
6, with sander ganoid wood plastic composite being carried out surface finish handles.So-called " grinding process " is to adopt mechanical means, forcing machine is extruded the ganoid wood plastic composite surface finish that makes fall skim, make its surface have the surface pattern that is similar to plank, to improve the effect of the imitative original real wood of wood plastic composite, make wood plastic composite with very strong woodiness touch.
Wood plastic composite-embodiment 1
70 parts of wood powders
5 parts in lime carbonate
25 parts of maleic anhydride graft polyolefine
3 parts of lubricants
1 part of cadmium pigment
0.2 part of carbon black
0.3 part of UV-1084
0.3 part of antioxidant BHT
Above-mentioned formulation material is added high-speed mixer to mix.
Compound is added the cocurrent and parallel twin screw extruder plastify granulation.The head section of used cocurrent and parallel twin screw extruder is not provided with pellet device, but directly extrudes, and extrudate cools off through whirlwind, removes water vapor simultaneously, is ground into pellet with pulverizer then.
To pulverize pellet and add conical double screw extruder, adopt the extrusion method extrusion moulding, make ganoid wood-plastic composite board.
With sander ganoid wood plastic composite is carried out surface finish and handles, make its surface have the surface pattern that is similar to plank, make outward appearance woodiness touch, color all the utmost point as the sheet material of natural timber.
Wood plastic composite-embodiment 2-8
Table 2: embodiment 2～8 proportioning raw materials
| Material name | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Wood powder | 75 | 60 | 62 | 70 | 70 | 60 | 65 |
| Lime carbonate | 15 | 10 | 20 | ||||
| The maleic anhydride graft polyolefine | 25 | 15 | 14 | 10 | 10 | 20 | 10 |
| PE or PP | 10 | 14 | 20 | 20 | 25 | ||
| Iron pigment | 1 | 1.5 | 2 | 1.8 | 1.5 | ||
| Cadmium pigment | 1 | 1.5 | |||||
| Carbon black | 0.15 | 0.2 | 0.1 | ||||
| Lubricant | 3 | 3 | 2.8 | 2.5 | 2.5 | 3.5 | 2.3 |
| UV-1084 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Antioxidant BHT | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
Claims (8)
1, a kind of maleic anhydride graft polyolefin wood-plastic composite is characterized in that having following raw material:
Plant fiber powder, maleic anhydride graft polyolefine and the auxilliary weight that adds plastics are 100 parts, and wherein plant fiber powder is 60～85 parts, and surplus for the maleic anhydride graft polyolefine adds plastics with auxilliary, wherein maleic anhydride graft polyolefine weight accounts for 40～100%;
Weight of additive is 2～6 parts, and wherein lubricant is 1.5～3 parts, and stablizer is 0.5～1 part, and surplus is tinting material.
2, maleic anhydride graft polyolefin wood-plastic composite according to claim 1 is characterized in that described plant fiber powder is 70～80 parts; Maleic anhydride graft polyolefine and auxilliary adding in the plastics,, maleic anhydride graft polyolefine weight accounts for 70～100%, and described auxilliary to add plastics be waste or used plastics.
3, maleic anhydride graft polyolefin wood-plastic composite according to claim 2 is characterized in that described waste or used plastics is waste and old PE and/or waste PP.
4, according to claim 1 or 2 or 3 described maleic anhydride graft polyolefin wood-plastic composites, it is characterized in that:
Described plant fiber powder is selected from one or more the mixture of arbitrary proportion in wood powder, bamboo powder, chaff powder, agricultural crop straw powder, the non-crop plants fiber powder;
Described maleic anhydride graft polyolefine is selected from the arbitrary proportion mixture of maleic anhydride graft PE, maleic anhydride graft PP or two kinds of graftss;
Described lubricant is selected from one or more the mixture in stearic acid, methyl stearate, butyl stearate, stearic amide, Palmiticacid acid amides, amine hydroxybenzene, ethylene bis stearamide, calcium stearate, Zinic stearas, lead laurate, whiteruss, solid paraffin, polyethylene wax, the oxidized polyethlene wax;
Described tinting material is selected from one or more the mixture in cadmium pigment, iron pigment, chromate pigments, the cobalt series pigments;
Described stablizer comprises photostabilizer and oxidation inhibitor, and photostabilizer is selected from UV-531, UV-1084, UV-774, and oxidation inhibitor is selected from BHT, 1010, DLTP, 330, SP.
5,, it is characterized in that described maleic anhydride graft polyolefine is maleic anhydride graft PE and the maleic anhydride graft PP that is made by waste and old PE and waste PP and maleic anhydride graft reaction according to claim 1 or 2 or 3 described maleic anhydride graft polyolefin wood-plastic composites.
6, maleic anhydride graft polyolefin wood-plastic composite according to claim 4 is characterized in that described maleic anhydride graft polyolefine is maleic anhydride graft PE and the maleic anhydride graft PP that is made by waste and old PE and waste PP and maleic anhydride graft reaction.
7, a kind of preparation method as the arbitrary maleic anhydride graft polyolefin wood-plastic composite of claim 1 to 6, it is characterized in that plant fiber powder is carried out drying, dried plant fiber powder is mixed in high-speed mixer with other raw material, plastify granulation with the cocurrent and parallel twin screw extruder again and get the wooden grain of moulding, use the conical double screw extruder extrusion moulding then, carry out surface finish at last and handle; Described grinding process is to adopt mechanical means, forcing machine is extruded the ganoid wood plastic composite surface finish that makes fall skim, makes its surface have the lines that is similar to natural timber.
8, the preparation method of maleic anhydride graft polyolefin wood-plastic composite according to claim 7, it is characterized in that: when described cocurrent and parallel twin screw extruder carries out the heating plasticizing granulation, head section is not provided with pellet device, but screw head is exposed, material is directly extruded, extrudate is delivered to cyclonic separator with fluidized and is cooled off, and removes moisture content and volatile matter, and pulverizing makes wood and moulds grain then.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100603198A CN101302349A (en) | 2008-04-03 | 2008-04-03 | Maleic anhydride grafted polypropylene wood-plastic composite material and preparation thereof |
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| CNA2008100603198A CN101302349A (en) | 2008-04-03 | 2008-04-03 | Maleic anhydride grafted polypropylene wood-plastic composite material and preparation thereof |
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| CN101302349A true CN101302349A (en) | 2008-11-12 |
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| WO2010081860A1 (en) * | 2009-01-15 | 2010-07-22 | Spanolux N.V. - Div. Balterio | Method of manufacturing floor panels containing wood/plastic composite, as well as such panels |
| CN101585970B (en) * | 2009-05-13 | 2011-07-06 | 杭州师范大学 | Polyolefin wood-plastic composite with low rate of water absorption |
| CN101698749B (en) * | 2009-11-03 | 2011-10-26 | 北京林业大学 | Wood-plastic composite material and prepration method thereof |
| CN102277001A (en) * | 2011-08-15 | 2011-12-14 | 江苏福瑞森塑木科技有限公司 | Micro nanometer-enhanced wood plastic composite board and preparation method thereof |
| CN103102572A (en) * | 2013-02-05 | 2013-05-15 | 四川大学 | Polyolefin wood-plastic composite material and preparation method thereof |
| CN103333513A (en) * | 2013-06-28 | 2013-10-02 | 湖州格林特木塑材料有限公司 | Wood-plastic composite material and preparation method thereof |
| CN104073010A (en) * | 2014-06-30 | 2014-10-01 | 江苏旭华圣洛迪建材有限公司 | Reactive type flame-retardant wood-plastic material and preparation method thereof |
| CN104582918A (en) * | 2012-03-19 | 2015-04-29 | Sh环球有限公司 | Plastic, for automotive interior parts, manufactured from biomass pellets, and method for manufacturing the plastic |
| CN106273302A (en) * | 2016-08-23 | 2017-01-04 | 张海 | A kind of preparation method of high-performance wood-plastic composite material |
| CN106336607A (en) * | 2016-08-26 | 2017-01-18 | 桐城市钰锦塑料包装有限公司 | Highly-water-resistant antibacterial wood-plastic composite material |
| CN106349629A (en) * | 2016-08-26 | 2017-01-25 | 桐城市钰锦塑料包装有限公司 | Anti-flaming wood-plastic composite |
| CN106366539A (en) * | 2016-08-26 | 2017-02-01 | 安徽钰锦生态木材料有限公司 | Anti-aging and anti-cold-shortness wood plastic composite material |
| CN106633997A (en) * | 2017-01-13 | 2017-05-10 | 扬州古籍线装文化有限公司 | Preparation method of engraving three-layer composite board |
| CN109852093A (en) * | 2017-11-30 | 2019-06-07 | 天津市川浩塑料制品有限公司 | A kind of regenerating and modifying plastic grain |
| CN110194863A (en) * | 2019-06-21 | 2019-09-03 | 东莞市腾卓美环保新材料科技有限公司 | The degradable plant fibre environment-friendly composite material of extrusion or plastic uptake thermoforming can be used |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010081860A1 (en) * | 2009-01-15 | 2010-07-22 | Spanolux N.V. - Div. Balterio | Method of manufacturing floor panels containing wood/plastic composite, as well as such panels |
| CN101585970B (en) * | 2009-05-13 | 2011-07-06 | 杭州师范大学 | Polyolefin wood-plastic composite with low rate of water absorption |
| CN101698749B (en) * | 2009-11-03 | 2011-10-26 | 北京林业大学 | Wood-plastic composite material and prepration method thereof |
| CN102277001A (en) * | 2011-08-15 | 2011-12-14 | 江苏福瑞森塑木科技有限公司 | Micro nanometer-enhanced wood plastic composite board and preparation method thereof |
| CN102277001B (en) * | 2011-08-15 | 2012-10-10 | 江苏福瑞森塑木科技有限公司 | Micro nanometer-enhanced wood plastic composite board and preparation method thereof |
| CN104582918A (en) * | 2012-03-19 | 2015-04-29 | Sh环球有限公司 | Plastic, for automotive interior parts, manufactured from biomass pellets, and method for manufacturing the plastic |
| CN103102572A (en) * | 2013-02-05 | 2013-05-15 | 四川大学 | Polyolefin wood-plastic composite material and preparation method thereof |
| CN103333513A (en) * | 2013-06-28 | 2013-10-02 | 湖州格林特木塑材料有限公司 | Wood-plastic composite material and preparation method thereof |
| CN104073010A (en) * | 2014-06-30 | 2014-10-01 | 江苏旭华圣洛迪建材有限公司 | Reactive type flame-retardant wood-plastic material and preparation method thereof |
| CN106273302A (en) * | 2016-08-23 | 2017-01-04 | 张海 | A kind of preparation method of high-performance wood-plastic composite material |
| CN106336607A (en) * | 2016-08-26 | 2017-01-18 | 桐城市钰锦塑料包装有限公司 | Highly-water-resistant antibacterial wood-plastic composite material |
| CN106349629A (en) * | 2016-08-26 | 2017-01-25 | 桐城市钰锦塑料包装有限公司 | Anti-flaming wood-plastic composite |
| CN106366539A (en) * | 2016-08-26 | 2017-02-01 | 安徽钰锦生态木材料有限公司 | Anti-aging and anti-cold-shortness wood plastic composite material |
| CN106633997A (en) * | 2017-01-13 | 2017-05-10 | 扬州古籍线装文化有限公司 | Preparation method of engraving three-layer composite board |
| CN106633997B (en) * | 2017-01-13 | 2019-01-22 | 扬州古籍线装文化有限公司 | A kind of preparation method of engraving three-layer composite board |
| CN109852093A (en) * | 2017-11-30 | 2019-06-07 | 天津市川浩塑料制品有限公司 | A kind of regenerating and modifying plastic grain |
| CN110194863A (en) * | 2019-06-21 | 2019-09-03 | 东莞市腾卓美环保新材料科技有限公司 | The degradable plant fibre environment-friendly composite material of extrusion or plastic uptake thermoforming can be used |
| CN113510820A (en) * | 2021-05-07 | 2021-10-19 | 东北林业大学 | Preparation method of light heat-preservation straw composite material |
| CN113510820B (en) * | 2021-05-07 | 2023-02-21 | 东北林业大学 | Preparation method of light heat-insulation straw composite material |
| CN115491007A (en) * | 2022-10-14 | 2022-12-20 | 东莞职业技术学院 | Rice hull powder reinforced polylactic acid 3D printing wire and preparation method thereof |
| CN115491007B (en) * | 2022-10-14 | 2023-09-01 | 东莞职业技术学院 | Rice hull powder reinforced polylactic acid 3D printing wire rod and preparation method thereof |
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