CN102260386B - Ecological composite material and preparation method thereof - Google Patents
Ecological composite material and preparation method thereof Download PDFInfo
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- CN102260386B CN102260386B CN201110146023XA CN201110146023A CN102260386B CN 102260386 B CN102260386 B CN 102260386B CN 201110146023X A CN201110146023X A CN 201110146023XA CN 201110146023 A CN201110146023 A CN 201110146023A CN 102260386 B CN102260386 B CN 102260386B
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- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010893 paper waste Substances 0.000 claims abstract description 81
- 239000000835 fiber Substances 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000002023 wood Substances 0.000 claims abstract description 25
- -1 polyethylene Polymers 0.000 claims abstract description 24
- 239000004698 Polyethylene (PE) Substances 0.000 claims abstract description 21
- 229920000573 polyethylene Polymers 0.000 claims abstract description 21
- UKRDPEFKFJNXQM-UHFFFAOYSA-N Vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims description 50
- 238000006011 modification reaction Methods 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000005453 pelletization Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N Butanol Natural products CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000005452 bending Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 3
- 239000000243 solution Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 235000012054 meals Nutrition 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 230000003068 static Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 235000013311 vegetables Nutrition 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 10
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N Iron(III) oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910000460 iron oxide Inorganic materials 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001105 regulatory Effects 0.000 description 5
- 241001319200 Ebo Species 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 230000000875 corresponding Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N Phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 210000002381 Plasma Anatomy 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- 240000006954 Cunninghamia lanceolata Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N Octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 229950002083 Octabenzone Drugs 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- 108010020147 Protein Corona Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920001587 Wood-plastic composite Polymers 0.000 description 1
- 229940089401 Xylon Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-J aluminum;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-J 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 238000011030 bottleneck Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000002596 correlated Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 210000001519 tissues Anatomy 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004642 transportation engineering Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011155 wood-plastic composite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Abstract
The invention discloses an ecological composite material, which consists of a basic material and an assistant, wherein the basic material comprises the following raw materials in percentage by weight: 12 to 45 percent of modified waste paper fiber powder, 8 to 30 percent of wood meal and 25 to 80 percent of polyethylene; the preparation method of the modified waste paper fiber powder comprises: cutting waste paper into pieces, directly soaking the waste paper into soaking solution, filtering, draining, performing heat treatment at 95 to 130 DEG C for 10 to 120 DEG C, obtaining modified waste paper pieces, crushing the modified waste paper pieces by high-speed mixing and shearing, filtering and drying to obtain modified waste paper fiber powder; and the soaking solution may be ethanol and water mixed solution of one or two of vinylsilane and vinylsiloxane oligomer. The ecological composite material has high static bending strength and creep resistance. The invention also discloses a method for preparing the material. The method is simple in operation and easy to control.
Description
Technical field
The present invention relates to field of compound material, be specifically related to a kind of ecological composite material and preparation method thereof.
Background technology
The development that utilizes technology along with reinforcement and the renewable resources of people's environmental protection consciousness, powerful in the global evolution impetus take the discarded synthesized polymer material that reclaims and natural macromolecular material as the ecological composite material of raw material preparation.At present, the synthesized polymer material that uses in this class ecological composite material (as section bar) comprises the thermoplasticss such as polyethylene, polyvinyl chloride, polystyrene; And natural macromolecular material is mainly some discarded vegetable fibres, comprises wood powder, bamboo powder, stalk, rice husk, Pericarppium arachidis hypogaeae etc.Both according to a certain percentage and add some processing aids, coupling agent etc. prepare corresponding section bar and goods through the melt blending molding device.The bending strength of this class composite material, hardness, wear resistance, water tolerance and Anti-moth-eating etc. have all surpassed solid wood or solid wood matrix material, and apparent color and luster is substantially close to solid wood material, product can be sawed, digs, follow closely simultaneously, use and maintenance is easy, is widely used in the fields such as outdoor building material (as floor, bed board, fence, guardrail), communications and transportation (as automotive trim, seat backup plate).Yet this class material also exists following common problem: creep-resistant property is poor, and dimensional stability is not good enough, and MOR is general, and especially toughness is far away from the excellence of timber performance.Therefore, be necessary further to research and develop this new green environment protection material, improve the quality of this series products, widen its Application Areas.
The polarity and the consequent intermolecular hydrogen bonding that have due to the vegetable fibre surface, dispersiveness and surface adhesion between hydrophilic filler and resin have been hindered, thereby affected the composite effect of the ecological composite material of this class, after the vegetable fibre loading level arrived certain value, the MOR of material, creep-resistant property and toughness drop were obvious.Therefore must carry out modification to vegetable fibre, eliminate or reduce its surface polarity degree, improve interface performance and the composite effect of composite material.
At present, vegetable fibre is carried out modification the physics and chemistry method of modifying is arranged.
Physical method mainly contains: 1) stretching, calendering, thermal treatment, blending etc., in order to structure and the surface properties that changes fiber, be convenient to the mechanical snap of fiber and matrix resin in recombination process; 2) discharge technology comprises the methods such as corona, low-temperature plasma, radiation.Corona treatment techniques is the functional group on activation fiber surface in a large number, changes the surface energy of fiber; The gas with various that the Low Temperature Plasma Treating technical basis is loaded with carries out the seriation surface treatment to xylon, makes fiber surface produce free radical and functional group; Discharge means is that inertial base resin such as polystyrene (PS), polyethylene (PE), polypropylene (PP) etc. are carried out modification; 3) gas explosion method: the method for gas instantaneous explosion causes that the form of vegetable fibre and structure change, thereby the intensity of vegetable fibre and specific surface area are increased.
Chemical modification is processed the quantity that vegetable fibre is intended to reduce the fiber surface hydroxy functional group, or introduces laterally crosslinked and compatible between vegetable fibre and resin matrix by the mode of physics or chemical bonding.Therefore the chemical modification processing is the method that fundamentally solves the two-phase material compatibility, is also a focus of studying at present both at home and abroad.Chemical modification method mainly contains:
1) compatilizer method, as making compatilizer with the grafting vegetable fibres such as maleic anhydride or maleic anhydride modified polyolefin resin, also can adopt with blend two-phase or multiphase can be well compatible general character compatilizer etc.; Especially the modified by maleic acid anhydride graft polymkeric substance is the comparatively successful a kind of compatilizer of commercial applications, just begin widespread use in ecological composite material as far back as the beginning of the nineties in last century, it or has obvious advantage no matter aspect the interface binding power that improves vegetable fibre and interlaminar resin and consistency aspect optimization processing technology.
2) coupling agent method as adopting the coupling agent treatment fibers such as silane, isocyanic ester, titanic acid ester, Aluminate, is improved the consistency of vegetable fibre and resin.Coupling agent is through hydrolysis, condensation and vegetable fibre, resin matrix generation chemical bonding or free radical reaction, make the interface binding power between modified plant fibers and resin strengthen, be conducive to the Uniform Dispersion of vegetable fibre in resin matrix, but preprocessing plant fibre must first be pulverized, grind to form certain fineness, then carries out the physical mixed stirring after adding corresponding coupling agent.
3) alkali metal soln facture, intensity and the specific surface area of increase wood powder fiber.The vegetable fibre cheap for some, that the xylogen equal size is more need first carry out alkali lye and remove, and this technique can increase production cost and need carry out the efforts at environmental protection of liquid waste disposal.
Xylogen in waste paper, starch and ash content equal size are lower, do not need to carry out alkali lye again and process; And the toughness of waste paper and tensile strength are good, have using value potential in the ecologic structure section bar.At present, waste paper is used for the report that is prepared with of ecological composite material and sticks with paste the mode moulding with a kind of molding or paper, and because the limitation of complete processing aspect, addition is less and production efficiency is low; And it is less as the research and development report that main raw material(s) prepares ecological composite material with waste paper and polyethylene, major cause is the pulverizing of reclaimed waste paper and the bottleneck that pretreatment technology becomes its development, therefore be necessary further to research and develop on the pretreatment technology of waste paper and corresponding composite preparation process, prepare the novel ecological composite material of excellent performance with lower cost, truly widen the comprehensive utilization field of this waste resource of waste paper.
Summary of the invention
The invention provides the ecological composite material of the excellent propertys such as a kind of MOR is high, creep-resistant property is good.
The present invention also provides a kind of preparation method of ecological composite material, and the method is simple to operate, is easy to control.
A kind of ecological composite material is made by body material and auxiliary agent, and described body material is comprised of the raw material of following weight percent:
Modification waste paper fibre powder 12%～45%
Wood powder 8%～30%
Polyethylene 25%～80%;
The preparation method of described modification waste paper fibre powder comprises: waste paper is divided fragmentate rear direct impregnation in steeping fluid, filtration drains rear 95 ℃～130 ℃ thermal treatments 10 minutes～120 minutes, obtain waste paper fragment after modification, waste paper fragment after modification is mixed to shear in the rotating speed of 1000 rev/mins of (rpm)～3500 rev/min pulverized 1 minute～10 minutes, filter, drying obtains modification waste paper fibre powder;
Described steeping fluid is one or both the alcohol-water mixture in vinyl silanes, vinyl silanes oligopolymer.
The main chemical compositions of reclaimed waste paper is Mierocrystalline cellulose and hemicellulose, and content of lignin is extremely low, and the toughness of waste paper is better, is difficult to obtain powdery substance by mechanical disintegration, and then has influence on it and poly melt blending is compound; On the other hand, contain a large amount of hydroxyls on the fiber glucose basic ring on waste paper surface, these hydroxyls have formed intramolecular hydrogen bond or intermolecular hydrogen bonding, make waste paper fibre show polarity and wetting ability, very weak with the poly interfacial adhesion of low surface energy, this has just hindered the effective dispersion of waste paper in the hydrophobic matrices material.Therefore, be necessary waste paper is carried out surface modification, and modification waste paper is ground into Powdered fibrous matter.For aforementioned key issue, the present invention analyzes by the surface tissue pattern to the reclaimed waste paper fiber, according to the requirement of preparation ecological composite material to pattern, fineness and the surface property of filling paper fiber, adopt the alcohol-water mixture dipping reclaimed waste paper of vinyl silanes and/or vinyl silanes oligopolymer, the hydrogen bond that on the surperficial natural fiber glucose of the silanol groups that produces after silane hydrolyzate and waste paper basic ring, hydroxyl forms produces the not ether covalent linkage Si-O-Cellulose (Mierocrystalline cellulose) of facile hydrolysis reverse through dehydration after high temperature drying thermal treatment.Waste paper fibre surface and poly interface binding power after surface modification drying is processed strengthen, melt extrude technique by back segment, the vinyl-functional on modification waste paper fibre surface can with polyethylene generation crosslinking reaction, further improve physical strength, dimensional stability and the creep-resistant property of matrix material.
Waste paper after modification thermal treatment can cut into powdery substance by high speed machine, and particle diameter is at 40 orders～120 orders.As shown in Figure 1, common reclaimed waste paper is difficult to be broken into after by high speed shear Powdered, and running and put forward high-revolving mode when long can obtain wadding fibrously, and the flocculence material tangles mutually, is difficult to carry out blend and melt extrude with polyethylene; And only need can obtain powdery substance by the high speed shear of short period of time through the waste paper after the inventive method modification thermal treatment, the powder diameter narrow distribution, as convenient with the polyethylene melt blending in Fig. 2, be easy at hydrophobic matrices material Uniform Dispersion.Simultaneously, the required energy consumption of mechanical disintegration significantly reduces.
In order to reach better invention effect, preferably:
Described dipping time is 1 minute～60 minutes.
The weight percent of described steeping fluid consists of:
In vinyl silanes, vinyl silanes oligopolymer one or both 0.05～5%
Alcohol 80～99%
Water surplus.
Alcohol in described steeping fluid is selected one or more in ethanol, propyl alcohol, butanols.
The pH value of described steeping fluid is preferably 4.5～5.5, can regulate by acid (as acetic acid) commonly used the pH value of steeping fluid.
After described modification, the waste paper fragment is preferably to mix in the incorgruous double worm mixer of 1000 rev/mins～2500 rev/mins to shear to pulverize at rotating speed.
The particle diameter of described modification waste paper fibre powder is 40 orders～120 orders, more preferably 80 orders～120 orders.
Described wood powder can be selected this area wood powders commonly used such as Chinese fir wood powder, and preferable particle size is 60 orders～120 purpose wood powders.
One or more in the auxiliary agents such as described selection of auxiliary lubricant, maleic anhydride grafted polyethylene, toner, anti ultraviolet agent.
Described lubricant can promote polymer melt impregnation of fibers and mixing between the two, helps melt to waltz through cross-head, reduces energy consumption, improves and extrudes processing output and quality of item; Can select Material Field lubricant commonly used, as one or more in ethylene bis stearic acid amide (EBS), the two amine hydroxybenzenes (EBO) of ethylene, ethylene bimonthly osmanthus acid amides (EBL) etc.
Described maleic anhydride grafted polyethylene can further improve wood powder and poly consistency.
Described toner be used for to be regulated the apparent colour of material, can select Material Field toner commonly used, as commercially available toner, such as one or more in carbon black, titanium dioxide, red iron oxide, iron oxide yellow, phthalocyanine green, phthalocyanine blue etc.
Described anti ultraviolet agent can improve the outdoor ageing-resistant performance of section bar, prevents variable color, fades, and can select Material Field anti ultraviolet agent commonly used, as commercially available anti ultraviolet agent, 2,4 dihydroxyl benzophenone, Octabenzone, 2-(2 '-hydroxyl-3 ' for example, 5 '-two uncle's phenyl)-5-chlorination benzotriazole, three (1,2,2,6,6-Pempiten base) phosphorous acid ester, 4-benzoyloxy-2, one or more in 2,6,6-tetramethyl piperidine etc.
The consumption of described auxiliary agent can be adjusted as required, be generally body material weight 8.5% in.
The preparation method of described ecological composite material comprises the following steps:
Modification waste paper fibre powder, wood powder, polyethylene and auxiliary agent are mixed extruding pelletization in equidirectional parallel double-screw extruder afterwards, and dry rear extrusion moulding makes ecological composite material;
Perhaps, wood powder, polyethylene and part of auxiliary are mixed extruding pelletization in equidirectional parallel double-screw extruder afterwards, after the pellet drying again with modification waste paper fibre powder and remaining auxiliary agent blend after extrusion moulding in conical double screw extruder, make ecological composite material.
The temperature of described extruding pelletization is preferably 180 ℃～220 ℃, and the temperature of extrusion moulding is preferably 180 ℃～210 ℃.
Compared with prior art, the present invention has following advantage:
Modification waste paper fibre powder of the present invention, wood powder are uniformly dispersed in the polyethylene base material, have increased waste paper fibre and the wood powder addition in ecological composite material, have reduced material cost.
The MOR of ecological composite material of the present invention is high, creep-resistant property good, has reached import analogous products level on technical feature, and technology is on the leading domestic level; Broken through the domestic technology limitation that reclaimed waste paper is prepared ecological composite material, realized that with own technology reclaimed waste paper prepares the manufacturing of ecological composite material, has broken international technology monopolization at home first.
Preparation method of the present invention is simple to operate, is easy to control, and production efficiency is high, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 be common reclaimed waste paper in incorgruous double worm mixer in the 2500rpm down cut audio-visual picture of the waste paper fibre powder that obtains after 2 minutes;
Fig. 2 is the audio-visual picture of the modification waste paper fibre powder that obtains in embodiment 1.
Embodiment
Embodiment 1
The preparation method of modification waste paper fibre powder is: divide the rear direct impregnation that fragmentates at the steeping fluid (pH=5.0 that is comprised of 0.5kg vinyl silanes, 94.5kg ethanol and 5kg water in waste paper, acetic acid is regulated) the middle dipping 30 minutes, filtration drains, obtain waste paper fragment after modification after 30 minutes through high temperature of 120 DEG C thermal treatment, waste paper fragment after modification is mixed to shear in incorgruous double worm mixer high speed (1500rpm) pulverized 5 minutes, it is 80 orders～120 purpose modification waste paper fibre powders that filtration, drying obtain particle diameter, as Fig. 2.
be 60 orders～80 purpose wood powders with the 2.0kg particle diameter, 5.0kg polyethylene and 0.1kg EBS, 0.2kg maleic anhydride grafted polyethylene, 0.01kg iron oxide yellow, 0.05kg2-hydroxyl-4-oxy-octyl benzophenone mix after in equidirectional parallel double-screw extruder at 180 ℃～210 ℃ (one section 180 ℃, two sections 185 ℃, three～five sections 200 ℃, six sections 210 ℃, seven sections 200 ℃) extruding pelletization, after the modification waste paper fibre powder that makes with 3.0kg again after the pellet drying and 0.2kg EBS blend at 180 ℃～210 ℃ (one section 180 ℃, two sections 190 ℃, three～four sections 200 ℃, five～six sections 210 ℃, seven sections 200 ℃) incorgruous conical double screw extruder extrusion moulding, make ecological composite material.
Embodiment 2
the preparation method of modification waste paper fibre powder is: divide the rear direct impregnation that fragmentates by 5kg vinyl silanes oligopolymer (SG-Si6490 in waste paper, NanJing Shuguang Chemical Group Co., Ltd.) steeping fluid (pH=4.5 of 80kg propyl alcohol and 15kg water composition, acetic acid is regulated) the middle dipping 1 minute, filtration drains, obtain waste paper fragment after modification after 10 minutes through high temperature 130 ℃ of thermal treatments, waste paper fragment after modification is mixed to shear in incorgruous double worm mixer high speed (1000rpm) pulverized 10 minutes, filter, it is 80 orders～100 purpose modification waste paper fibre powders that drying obtains particle diameter.
be 80 orders～100 purpose wood powders with the 0.8kg particle diameter, 8kg polyethylene and 0.02kg EBO, 0.08kg maleic anhydride grafted polyethylene, 0.01kg iron oxide yellow, 0.03kg2-hydroxyl-4-oxy-octyl benzophenone mix after in equidirectional parallel double-screw extruder at 180～210 ℃ (one section 180 ℃, two sections 185 ℃, three～five sections 200 ℃, six sections 210 ℃, seven sections 200 ℃) extruding pelletization, after the pellet drying again with 1.2kg modification waste paper fibre powder and 0.03kg EBO blend after at 180 ℃～210 ℃ (one section 180 ℃, two sections 190 ℃, three～four sections 200 ℃, five～six sections 210 ℃, seven sections 200 ℃) incorgruous conical double screw extruder extrusion moulding, make ecological composite material.
Embodiment 3
the preparation method of modification waste paper fibre powder is: divide the rear direct impregnation that fragmentates by the 0.03kg vinyl silanes in waste paper, 0.02kg vinyl silanes oligopolymer (SG-Si6490, NanJing Shuguang Chemical Group Co., Ltd.), steeping fluid (the pH=5.5 that 99kg propyl carbinol and 0.95kg water form, acetic acid is regulated) the middle dipping 60 minutes, filtration drains, obtain waste paper fragment after modification after 120 minutes through high temperature 95 ℃ of thermal treatments, waste paper fragment after modification is mixed to shear in incorgruous double worm mixer high speed (2500pm) pulverized 1 minute, filter, it is 40 orders～80 purpose modification waste paper fibre powders that drying obtains particle diameter.
be 100 orders～120 purpose wood powders with the 1.0kg particle diameter, 2.0kg modification waste paper fibre powder, 7.0kg polyethylene and 0.15kg EBL, 0.1kg maleic anhydride grafted polyethylene, 0.01kg iron oxide yellow, 0.04kg2-hydroxyl-4-oxy-octyl benzophenone mix after in equidirectional parallel double-screw extruder at 180～210 ℃ (one section 180 ℃, two sections 190 ℃, three～five sections 200 ℃, six sections 210 ℃, seven sections 200 ℃) extruding pelletization, after the pellet drying at 180 ℃～210 ℃ (one section 180 ℃, two sections 190 ℃, three～five sections 210 ℃, six sections 200 ℃, seven sections 190 ℃) the single screw extrusion machine extrusion moulding, make ecological composite material.
Embodiment 4
the preparation method of modification waste paper fibre powder is: divide the rear direct impregnation that fragmentates by the 0.6kg vinyl silanes in waste paper, 1.2kg vinyl silanes oligopolymer (SG-Si6490, NanJing Shuguang Chemical Group Co., Ltd.), 88.6kg the steeping fluid (pH=5.0 that ethanol and 9.6kg water form, acetic acid is regulated) the middle dipping 20 minutes, filtration drains, obtain waste paper fragment after modification after 60 minutes through high temperature of 120 DEG C thermal treatment, waste paper fragment after modification is mixed to shear in incorgruous double worm mixer high speed (1500rpm) pulverized 5 minutes, filter, it is 80 orders～120 purpose modification waste paper fibre powders that drying obtains particle diameter.
be 80 orders～100 purpose wood powders with the 3.0kg particle diameter, 2.5kg polyethylene and 0.12kg EBS, 0.3kg maleic anhydride grafted polyethylene, 0.01kg iron oxide yellow, 0.03kg2-hydroxyl-4-oxy-octyl benzophenone, 0.02kg three (1, 2, 2, 6, 6-Pempiten base) phosphorous acid ester mix after in equidirectional parallel double-screw extruder at 180～220 ℃ (one section 180 ℃, two sections 185 ℃, three～four sections 200 ℃, five sections 210 ℃, six sections 220 ℃, seven sections 200 ℃) extruding pelletization, after the pellet drying again with 4.5kg modification waste paper fibre powder and 0.28kg EBO blend after at 180 ℃～210 ℃ (one section 180 ℃, two sections 190 ℃, three～four sections 200 ℃, five～six sections 210 ℃, seven sections 200 ℃) incorgruous conical double screw extruder extrusion moulding, make ecological composite material.
Comparative Examples 1
be 60 orders～80 purpose wood powders with the 3.0kg particle diameter, 1.0kg particle diameter is 60 orders～80 purpose bamboo powder, 1.0kg particle diameter is 40 orders～60 purpose straw powder, 5.0kg polyethylene and 0.3kg EBS, 0.5kg maleic anhydride grafted polyethylene, 0.01kg iron oxide yellow, 0.05kg2-hydroxyl-4-oxy-octyl benzophenone mix after in equidirectional parallel double-screw extruder at 180～210 ℃ (one section 180 ℃, two sections 185 ℃, three～five sections 200 ℃, six sections 210 ℃, seven sections 200 ℃) extruding pelletization, after the pellet drying at 180 ℃～210 ℃ (one section 180 ℃, two sections 190 ℃, three～four sections 200 ℃, five～six sections 210 ℃, seven sections 200 ℃) the single screw extrusion machine extrusion moulding, make Wood-plastic profiles.
Ecological composite material and common ecological composite material (Wood-plastic profiles that Comparative Examples 1 makes) and same kind of products at abroad (Trex Company that embodiment 1-5 is made, Escapes Decking) correlated performance relatively, examination criteria is according to LY/T 1613-2004 " extruding wood-plastic composite panel ":
As seen ecological composite material of the present invention has reached the requirement of PE outdoor flooring, can be used for preparing the PE outdoor flooring.
Claims (9)
1. an ecological composite material, made by body material and auxiliary agent, it is characterized in that, described body material is comprised of the raw material of following weight percent:
Modification waste paper fibre powder 12% ~ 45%
Wood powder 8% ~ 30%
Polyethylene 25% ~ 80%;
The preparation method of described modification waste paper fibre powder comprises: waste paper is divided fragmentate rear direct impregnation in steeping fluid, filtration drains rear 95 ℃ ~ 130 ℃ thermal treatments 10 minutes ~ 120 minutes, obtain waste paper fragment after modification, waste paper fragment after modification is mixed shear in the rotating speed of 1000 rev/mins ~ 3500 rev/mins and pulverized 1 minute ~ 10 minutes, filtration, drying obtain modification waste paper fibre powder;
Described steeping fluid is one or both the alcohol-water mixture in vinyl silanes, vinyl silanes oligopolymer;
The pH value of described steeping fluid is 4.5 ~ 5.5.
2. ecological composite material according to claim 1, is characterized in that, described dipping time is 1 minute ~ 60 minutes.
3. ecological composite material according to claim 1, is characterized in that, the weight percent of described steeping fluid consists of:
In vinyl silanes, vinyl silanes oligopolymer one or both 0.05% ~ 5%
Alcohol 80% ~ 99%
Water surplus.
4. according to claim 1 or 3 described ecological composite materials, is characterized in that, the alcohol in described steeping fluid is one or more in ethanol, propyl alcohol, butanols.
5. ecological composite material according to claim 1, is characterized in that, after described modification, the waste paper fragment is to mix in the incorgruous double worm mixer of 1000 rev/mins ~ 2500 rev/mins to shear to pulverize at rotating speed.
6. ecological composite material according to claim 1, is characterized in that, the particle diameter of described modification waste paper fibre powder is 40 orders ~ 120 orders;
Perhaps, the particle diameter of described wood powder is 60 orders ~ 120 orders.
7. ecological composite material according to claim 6, is characterized in that, the particle diameter of described modification waste paper fibre powder is 80 orders ~ 120 orders.
8. the preparation method of according to claim 1 ~ 7 described ecological composite materials of any one comprises the following steps:
Modification waste paper fibre powder, wood powder, polyethylene and auxiliary agent are mixed extruding pelletization in equidirectional parallel double-screw extruder afterwards, and dry rear extrusion moulding makes ecological composite material;
Perhaps, wood powder, polyethylene and part of auxiliary are mixed extruding pelletization in equidirectional parallel double-screw extruder afterwards, after the pellet drying again with modification waste paper fibre powder and remaining auxiliary agent blend after extrusion moulding in conical double screw extruder, make ecological composite material.
9. the preparation method of ecological composite material according to claim 8, is characterized in that, the temperature of described extruding pelletization is 180 ℃ ~ 220 ℃, and the temperature of extrusion moulding is 180 ℃ ~ 210 ℃.
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| CN103289198A (en) * | 2013-06-13 | 2013-09-11 | 江苏中恒宠物用品股份有限公司 | Wood-plastic composite material and preparation method thereof |
| CN103319785A (en) * | 2013-06-24 | 2013-09-25 | 华东理工大学 | Method for preparing biomass composite from recycled waste paper |
| CN103804939B (en) * | 2014-02-14 | 2016-06-15 | 唐山市唯森新材料有限公司 | Novel ecological wood and preparation method thereof |
| CN104774390A (en) * | 2015-04-25 | 2015-07-15 | 桂林理工大学 | Method for preparing polypropylene-based wood-plastic composite material by using wood sawdust flour |
| CN106245394A (en) * | 2016-07-26 | 2016-12-21 | 华南农业大学 | A kind of preparation method of paper powder |
| CN110373953A (en) * | 2019-07-15 | 2019-10-25 | 上海永玺环境科技有限公司 | A kind of manufacturing method that railing is isolated |
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| CN1255427A (en) * | 1998-12-03 | 2000-06-07 | 中国石化齐鲁石油化工公司 | Compound plastic plate and its making method |
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| 废纸/ 再生高密度聚乙烯复合材料的力学性能研究;张春红等;《塑料工业》;20080930;第36卷(第9期);第52-55页 * |
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