CN105419063A - Degradable wood-plastic composite material and preparation method thereof - Google Patents
Degradable wood-plastic composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention provides a degradable wood-plastic composite material and a preparation method thereof. The method includes the step that a non-degradable plastic base material, wood fiber powder, an oxidizing-bio-degradable additive and an anti-oxidization agent are mixed and processed to obtain the degradable wood-plastic composite material, wherein the mass ratio of the non-degradable plastic base material to the wood fiber powder is (90-20):(10-80), the oxidizing-bio-degradable additive accounts for 1-20% of the total mass of the non-degradable plastic base material and the wood fiber powder, and the anti-oxidization agent accounts for 0.1-10% of the total mass of the non-degradable plastic base material and the wood fiber powder. A certain quantity of the oxidizing-bio-degradable additive is added, so that the wood-plastic composite material has the oxidization and biodegradation capacity, and the degradation time of the material is controllable. When the service life of the wood-plastic composite material is up, oxidizing-bio-degradation can be carried out in the natural environment, and environment pollution is small. Compared with a common wood-plastic composite material, the wood-plastic composite material has the same physicochemical properties in use and is wide in application range.
Description
Technical field
The present invention relates to wood plastic composite technical field, particularly relate to a kind of degradable wood plastic composite and preparation method thereof.
Background technology
Wood plastic composite, refer to low value or discarded biological material, if wood powder, rice husk, straw powder etc. are main raw material, utilize the feature of the macromolecule interfacial principles of chemistry and filling plastic modification, compounding a certain proportion of plastic matrix, through professional art breading, the type material of the processing and utilization a kind of capable of circulation of machine-shaping.It has possessed the multiple advantage of natural phant and synthetic plastics two kinds of base mateirals simultaneously, obtains increasingly extensive application in industries such as building materials, furniture and logistics packagings.
But due to the non-biodegradable of conventional plastic base material, Wood-plastic material goods can bring many problem of environmental pollutions after discarding.
Summary of the invention
In view of this, the object of the application is to provide a kind of degradable wood plastic composite and preparation method thereof, and wood plastic composite provided by the invention has good use properties, and degradable, is beneficial to environmental protection simultaneously.
The invention provides a kind of degradable wood plastic composite, comprising:
Non-degradable plastic matrix, wood fiber powder, oxidation-bio-degradable additive and oxidation inhibitor;
The mass ratio of described non-degradable plastic matrix and wood fiber powder is (90 ~ 20): (10 ~ 80);
The quality of described oxidation-bio-degradable additive accounts for 1% ~ 20% of non-degradable plastic matrix and wood fiber powder total mass;
The quality of described oxidation inhibitor accounts for 0.1% ~ 10% of non-degradable plastic matrix and wood fiber powder total mass.
Preferably, the mass ratio of described non-degradable plastic matrix and wood fiber powder is (80 ~ 30): (20 ~ 70).
Preferably, the quality of described oxidation-bio-degradable additive accounts for 2% ~ 15% of non-degradable plastic matrix and wood fiber powder total mass.
Preferably, the quality of described oxidation inhibitor accounts for 0.5% ~ 5% of non-degradable plastic matrix and wood fiber powder total mass.
Preferably, described non-degradable plastic matrix is selected from one or more in polyethylene, polypropylene, polyvinyl chloride and polystyrene.
Preferably, described oxidation-bio-degradable additive comprises nano transition metal inorganics, transition metal salt, poly-basic organic acid and plastic substrate.
Preferably, described oxidation-bio-degradable additive obtains in accordance with the following methods:
Mix in a solvent by transition metal salt and poly-basic organic acid and containing the presoma of transition metal, obtain mixed solution;
After described mixed solution is made inverse micellar solution, carry out successively being incubated, ageing be separated, obtain polynary nanometer particle;
Carry out extruding pelletization by after described polynary nanometer particle and plastic substrate mixing, obtain oxidation-bio-degradable additive.
The invention provides a kind of preparation method of degradable wood plastic composite, comprise the following steps:
After blended to non-degradable plastic matrix, wood fiber powder, oxidation-bio-degradable additive and oxidation inhibitor, carry out forming process, obtain degradable wood plastic composite;
The mass ratio of described non-degradable plastic matrix and wood fiber powder is (90 ~ 20): (10 ~ 80);
The quality of described oxidation-bio-degradable additive accounts for 1% ~ 20% of non-degradable plastic matrix and wood fiber powder total mass;
The quality of described oxidation inhibitor accounts for 0.1% ~ 10% of non-degradable plastic matrix and wood fiber powder total mass.
Preferably, be specially: by non-degradable plastic matrix and oxidation-bio-degradable additive and oxidation inhibitor mixing, obtain compound;
After being mixed with wood fiber powder by described compound, carry out forming process, obtain degradable wood plastic composite.
Preferably, the temperature of described forming process is 150 DEG C ~ 250 DEG C, and the time of described forming process is 10min ~ 1h.
Compared with prior art, plastic components in wood plastic composite provided by the invention is common non-degradable plastic matrix, wood substance component is with this xylophyta fiber of wood fiber powder for main raw material, and the mass ratio of described non-degradable plastic matrix and wood fiber powder is (90 ~ 20): (10 ~ 80); The present invention utilizes oxidation-bio-degradable technology, adds small amounts-bio-degradable additive in wood plastic composite, and the quality of described oxidation-bio-degradable additive accounts for 1% ~ 20% of non-degradable plastic matrix and wood fiber powder total mass; The present invention also add account for non-degradable plastic matrix and wood fiber powder total mass 0.1% ~ 10% oxidation inhibitor, make the degradable wood plastic composite of a kind of novel environment friendly.The present invention with the addition of a certain amount of oxidation-bio-degradable additive, uses oxidation-biodegradation plastic technology, make wood plastic composite have oxidative degradation and biodegradable ability concurrently, and its degradation time is controlled; When carrying out being oxidized-biological degradation in physical environment after wood plastic composite reaches work-ing life, thus can not to environment.Meanwhile, wood plastic composite of the present invention in use has the physicochemical property identical with normal wood plastic composite materials and use properties, as water-intake rate is low, and not easily strain cracking, Anti-moth-eating goes mouldy; Have that mechanical property is high, light weight, protection against the tide, acid and alkali-resistance, corrosion-resistant and be convenient to the features such as cleaning, can substitute the uses such as log, plastics and aluminium alloy in a lot of field, market application foreground is extensive.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of degradable wood plastic composite, comprising:
Non-degradable plastic matrix, wood fiber powder, oxidation-bio-degradable additive and oxidation inhibitor;
The mass ratio of described non-degradable plastic matrix and wood fiber powder is (90 ~ 20): (10 ~ 80);
The quality of described oxidation-bio-degradable additive accounts for 1% ~ 20% of non-degradable plastic matrix and wood fiber powder total mass;
The quality of described oxidation inhibitor accounts for 0.1% ~ 10% of non-degradable plastic matrix and wood fiber powder total mass.
Wood plastic composite provided by the invention has the advantage that common non-degradable wood plastic composite has, as good processing characteristics, good strength property, water-fast and corrosion resistance nature etc.; And described wood plastic composite can carry out being oxidized-biological degradation after reaching work-ing life in physical environment, fundamentally solves the environmental issue of plastic pollution.
Wood plastic composite provided by the invention comprises non-degradable plastic matrix, and it belongs to can not by the parts of plastics of natural degradation.One or more preferably in polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC) and polystyrene (PS) of described non-degradable plastic matrix, are more preferably polyethylene.In one embodiment of the invention, described non-degradable plastic matrix is the polyethylene (PE) that this area is commonly used, and comprises high density polyethylene(HDPE) (HDPE) and Low Density Polyethylene (LDPE).The source of the present invention to described non-degradable plastic matrix is not particularly limited, and can adopt commercially available prod, and as conventional polythene material, number-average molecular weight scope can 50,000 ~ 300,000, and be preferably 50,000 ~ 150,000, fusing point is 90 DEG C ~ 130 DEG C.
Wood plastic composite provided by the invention comprises wood fiber powder, and it is wood substance component.Wood fibre of the present invention is xylophyta fiber, lumber fibre, and wood fiber powder can be the flour that the process such as drying, pulverizing such as bark, timber, wood chip are formed, also referred to as wood powder.Described wood fiber powder is well known to those skilled in the art, and can adopt commercially available prod; The granularity of wood fiber powder of the present invention can be 40 ~ 1000 orders, and in an embodiment of the present invention, described wood fiber powder was the wood fiber powder of 40 mesh sieves.
In the present invention, the mass ratio of described non-degradable plastic matrix and wood fiber powder is (90 ~ 20): (10 ~ 80), is preferably (80 ~ 30): (20 ~ 70).In one embodiment of the invention, the mass ratio of described non-degradable plastic matrix and wood fiber powder is 60:40.In one embodiment of the invention, described non-degradable plastic matrix is PE, and the mass ratio of itself and wood fiber powder is 60:40.
Wood plastic composite provided by the invention comprises oxidation-bio-degradable additive; So-called oxidation-the bio-degradable of the present invention passes through oxidative degradation in the envrionment conditionss such as light, heat or oxygen, make common plastics such as polyolefinic molecular weight be reduced to less than 10,000, then the polymer segment of small-molecular-weight is utilized by microorganism and progressively carries out biological degradation.In the present invention, described oxidation-bio-degradable additive to make in wood plastic composite the parts of plastics of natural degradation can not realize natural degradation, finally be degraded into carbonic acid gas and water, thus fundamentally solve the problem of existing wood plastic composite " plastic pollution ".
In the present invention, the quality of described oxidation-bio-degradable additive accounts for 1% ~ 20% of non-degradable plastic matrix and wood fiber powder total mass, is preferably 2% ~ 15%, is more preferably 3% ~ 10%.In the present invention, the numbers of particles of every 10g degradable master batch can between 200 ~ 600.In one embodiment of the invention, described oxidation-bio-degradable additive is oxidation-bio-degradable polypropylene agglomerate (EBPmas-PP) or oxidation-bio-degradable polyethylene master batch (EBPmas-PE).
In the present invention, described oxidation-bio-degradable additive preferably includes nano transition metal inorganics, transition metal salt, poly-basic organic acid and plastic substrate.This oxidation-bio-degradable additive is nano-high molecule polynary pair of degradant additive, and the present invention preferably adopts a small amount of this additive to be mixed in straw wood-plastic composite material, can obtain better degradation effect.
In an embodiment of the present invention, described oxidation-bio-degradable additive comprises nano transition metal inorganics, and it is ultraviolet catalytic degraded composition, and particle diameter can between 5nm ~ 900nm.Described nano transition metal inorganics preferably from nano transition metal oxides or nano transition metal sulfide, is more preferably nano-TiO
2, nano-ZnO, nanometer ZnS, the mixture of a kind of inorganics in nano-tube/CdS and nano PbS or multiple formation or mixture be (as Ti
xzn
yo
2x+y, x, y and 2x+y are wherein atomic ratio), most preferably be nano-TiO
2.Described oxidation-bio-degradable additive preferably includes the nano transition metal inorganics of 0.1wt% ~ 10wt%, more preferably comprises the nano transition metal inorganics of 1wt% ~ 8wt%.
Described oxidation-bio-degradable additive can comprise transition metal salt, and it is visible light catalytic oxidation degraded and heat catalytic oxidation degraded composition.Transition metal in described transition metal salt is preferably from cobalt, iron, vanadium, manganese, cerium or zinc; That is, described transition metal salt comprises water-soluble organic acid salt or the inorganic acid salt of iron, cobalt, vanadium, manganese, cerium, zinc etc.In an embodiment of the present invention, described transition metal salt can the formate of chosen from Fe, cobalt, vanadium, manganese, cerium or zinc, acetate, nitrate, vitriol, hydrochloride or acetylacetonate, as ironic formiate, ironic acetate, iron nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, ferric sulfate, sulfuric acid two ammonium iron, ferric acetyl acetonade, iron(ic) chloride etc.Described oxidation-bio-degradable additive preferably includes the transition metal salt of 1wt% ~ 10wt%, more preferably comprises the transition metal salt of 3wt% ~ 8wt%.
Described oxidation-bio-degradable additive can comprise poly-basic organic acid, and it is for helping oxidative degradation composition, and consumption can be 1% ~ 10% of additive gross weight, is preferably 3% ~ 8%.Described poly-basic organic acid be preferably in 1,3-trimethylenedinitrilo-tertraacetic acid (PDTA), tartrate, fumaric acid, oxysuccinic acid and citric acid one or more, be more preferably citric acid.The source of the present invention to described poly-basic organic acid etc. is not particularly limited, and adopts commercially available prod.
Described oxidation-bio-degradable additive comprises the plastic substrate of surplus, preferably from polyolefine, polyaniline or polyester, be more preferably in polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene resin, polyethylene terephthalate and polybutylene terephthalate one or more, most preferably be polyethylene, polypropylene, polystyrene or polyvinyl chloride.The present invention preferably adopts containing polyolefinic oxidation-bio-degradable additive, and the consistency of itself and wood plastic composite is better, is beneficial to application.The source etc. of the present invention to described plastic substrate is not particularly limited, and adopts commercially available prod.
Described oxidation-bio-degradable additive also can comprise tensio-active agent; It preferably includes the tensio-active agent of 1wt% ~ 10wt%, more preferably comprises the tensio-active agent of 3wt% ~ 5wt%.Described tensio-active agent includes but not limited to the two different pungent vinegar sodium sulfonate (AOT) of cetyl trimethylammonium bromide (CTAB), palmityl trimethyl ammonium chloride (CTAC), Trimethyllaurylammonium bromide (DTAB), Dodecyl trimethyl ammonium chloride (DTAC), sodium lauryl sulphate (SDS), amber, Sodium dodecylbenzene sulfonate (DBS), fatty alcohol-polyoxyethylene ether (AE) and alkylphenol polyoxyethylene (APE).In one embodiment of the invention, described oxidation-bio-degradable additive comprises hexadecyl trimethyl ammonium bromide.
Above-mentioned nano transition metal inorganics, transition metal salt, poly-basic organic acid and plastic substrate can mix by the embodiment of the present invention, through extruding pelletization, obtain oxidation-bio-degradable additive.Wherein, described mixing is preferably carried out in homogenizer, and the time of stirring is generally 1 minute ~ 3 minutes.The embodiment of the present invention can adopt dual-screw pelletizer group to carry out extruding pelletization; The temperature respectively extruding section is generally 50 DEG C ~ 250 DEG C, extrudes revolution and can be 25 revs/min ~ 450 revs/min.
The source of the present invention to described oxidation-bio-degradable additive is not particularly limited, commercially available prod can be adopted, but preferably obtain in accordance with the following methods: mix in a solvent by transition metal salt and poly-basic organic acid and containing the presoma of transition metal, obtain mixed solution; After described mixed solution is made inverse micellar solution, carry out successively being incubated, ageing be separated, obtain polynary nanometer particle; Carry out extruding pelletization by after described polynary nanometer particle and plastic substrate mixing, obtain oxidation-bio-degradable additive.
The embodiment of the present invention by transition metal salt and poly-basic organic acid and can mix containing the precursor water solution of transition metal, is then mixed with the organic solution containing tensio-active agent by the mixed solution obtained, and forms reverse micelle system.In the above-described embodiments, the content of described transition metal salt and poly-basic organic acid, with described content is consistent above, does not repeat them here.The described presoma containing transition metal, namely by reacting the material of obtained transition metal inorganics, can be selected from water-soluble transition metal salt, comprising TiCl
4, Ti (NO
3)
4, Ti (SO
4)
2, TiOSO
4, ZnCl
2, Zn (NO
3)
2, ZnSO
4, CdCl
2, Cd (NO
3)
2, CdSO
4, PbCl
2, Pd (NO
3)
2or PbSO
4.
The embodiment of the present invention adopts the organic solution containing tensio-active agent, makes mixed solution make inverse micellar solution.The content of described tensio-active agent is with described content is consistent above; Described is conventional containing organic solvent in the organic solution of tensio-active agent, as one or more in normal hexane, toluene, hexanaphthene, octane-iso and kerosene, is preferably kerosene; And wherein the concentration of tensio-active agent can be 0.02mol/L ~ 1.0mol/L, be preferably 0.1mol/L ~ 0.8mol/L.In the reverse micelle mixed solution formed, in described transition metal salt, the solubility of transition metal ion can be 0.01mol/L ~ 200mol/L, is preferably 1mol/L ~ 100mol/L; The concentration of described poly-basic organic acid can be 0.01mol/L ~ 200mol/L, is preferably 1mol/L ~ 100mol/L; The concentration of the described presoma containing transition metal can be 0.01mol/L ~ 200mol/L, is preferably 1mol/L ~ 100mol/L.
After obtaining reaction micellar solution, the embodiment of the present invention by it at certain temperature held for some time, then can carry out ageing, obtains the suspension liquid containing polynary nanometer particle.In the above-described embodiments, the temperature of described insulation can be 80 DEG C ~ 90 DEG C, is preferably 90 DEG C; The time of described insulation can be 6h ~ 8h, is preferably 6h.Described ageing can be carried out under having the condition of protection of inert gas in autoclave; The temperature of described ageing can be 140 DEG C ~ 150 DEG C, is preferably 145 DEG C; The time of described ageing can be 40h ~ 50h, is preferably 45h ~ 48h, is more preferably 48h.
After obtaining the suspension liquid containing polynary nanometer particle, it can be carried out centrifugation, drying by the embodiment of the present invention successively, obtains polynary nanometer particle powder.Wherein, described centrifugation and drying are technique means well known to those skilled in the art, and the present invention is not particularly limited.
The embodiment of the present invention is carried out extruding pelletization, is obtained oxidation-bio-degradable additive after the polynary nanometer particle powder obtained and plastic substrate being mixed.Wherein, described mixing is preferably carried out in homogenizer, and the time of stirring is generally 1 minute ~ 3 minutes.The embodiment of the present invention can adopt dual-screw pelletizer group to carry out extruding pelletization; The temperature respectively extruding section is generally 50 DEG C ~ 250 DEG C, extrudes revolution and can be 25 revs/min ~ 450 revs/min.
In addition, the embodiment of the present invention also can by transition metal salt and poly-basic organic acid aqueous solution, then the mixed solution obtained is mixed with the organic solution containing tensio-active agent, then the reverse micelle system formed is mixed with the presoma organic solution containing transition metal, obtain reacting micellar solution.In the present embodiment, the described presoma containing transition metal can be selected from oil soluble transition metallorganics, comprises Ti (OC
4h
9)
4, titanium isopropylate, isooctyl alcohol titanium, sec.-propyl three oleic acid acyloxy titanic acid ester, methyl ethyl diketone titanium oxide, tetraethyl titanate, metatitanic acid orthocarbonate, tetra-tert titanic acid ester or three Unimac 5680 isopropyl titanates.Described is conventional containing organic solvent in the presoma organic solution of transition metal, as one or more in normal hexane, toluene, hexanaphthene, octane-iso and kerosene, is preferably kerosene.The reverse micelle system formed mixes with the presoma organic solution containing transition metal by the embodiment of the present invention, preferably stirs 0.5h ~ 5h, more preferably stirs 1h ~ 4h.
In this method of the embodiment of the present invention, all the other steps can be as previously mentioned.That is, the inverse micellar solution finally made is carried out successively be incubated, ageing be separated, obtain polynary nanometer particle; Carry out extruding pelletization by after described polynary nanometer particle and plastic substrate mixing, obtain oxidation-bio-degradable additive.
The oxidation that the embodiment of the present invention prepares-bio-degradable additive can be called environment universality degradative plastics master batch (degradative plastics master batch), this oxidation-bio-degradable master batch has nano-high molecule multiple elements design structure, the degradation effect added in wood plastic composite is better, and the use properties of matrix material is also unaffected.The embodiment of the present invention can adopt the model of Shandong Ecology Benign Plastics Technology Co., Ltd. to be the oxidation-bio-degradable master batch of EBPmas-PP-1502, EBPmas-PP-1501 or EBPmas-PE-1501.
Except oxidation-bio-degradable additive, wood plastic composite provided by the invention comprises oxidation inhibitor.Different according to performance requirement, described wood plastic composite can add the oxidation inhibitor of different amount; The quality of described oxidation inhibitor accounts for 0.1% ~ 10% of non-degradable plastic matrix and wood fiber powder total mass, is preferably 0.5% ~ 5%.The present invention is not particularly limited described oxidation inhibitor, as adopted Hinered phenols antioxidant BHT, 1010 and 1076, or adopts suffocated amine antioxidant 944 and 622, can also adopt irgasfos 168, oxidation inhibitor 215 and oxidation inhibitor 225 etc.In addition, wood plastic composite provided by the invention also can comprise some additives for normal wood plastic composite materials; The present invention is not particularly limited this.
Accordingly, the invention provides a kind of preparation method of degradable wood plastic composite, comprise the following steps:
After blended to non-degradable plastic matrix, wood fiber powder, oxidation-bio-degradable additive and oxidation inhibitor, carry out forming process, obtain degradable wood plastic composite;
The mass ratio of described non-degradable plastic matrix and wood fiber powder is (90 ~ 20): (10 ~ 80);
The quality of described oxidation-bio-degradable additive accounts for 1% ~ 20% of non-degradable plastic matrix and wood fiber powder total mass;
The quality of described oxidation inhibitor accounts for 0.1% ~ 10% of non-degradable plastic matrix and wood fiber powder total mass.
The embodiment of the present invention, by after blended to the non-degradable plastic matrix of said ratio, wood fiber powder and oxidation-bio-degradable additive and oxidation inhibitor etc., carries out forming process, obtained degradable straw wood-plastic composite material.The present invention is preferably specially: by non-degradable plastic matrix and oxidation-bio-degradable additive and oxidation inhibitor mixing, obtain compound; After being mixed with wood fiber powder by described compound, carry out forming process, obtain degradable wood plastic composite.
In the present invention, described non-degradable plastic matrix, wood fiber powder are consistent with previously described content with the content of the raw materials such as oxidation-bio-degradable additive, do not repeat them here.The embodiment of the present invention is by non-degradable plastic matrix and oxidation-bio-degradable additive and oxidation inhibitor Homogeneous phase mixing; The time of described mixing is preferably 1min ~ 20min, is more preferably 10min ~ 20min.The compound obtained mixes with wood fiber powder by the embodiment of the present invention, through hot pressing compound or the forming process different modes such as melt extruding, makes and has oxidative degradation and biodegradable wood plastic composite concurrently.In an embodiment of the present invention, the temperature of described forming process is 150 DEG C ~ 250 DEG C, is preferably 180 DEG C ~ 220 DEG C; The time of described forming process is 10min ~ 1h, is preferably 20min ~ 50min.For PP, the temperature of forming process is generally 150 ~ 190 DEG C, is preferably 175 DEG C; Molding time is preferably 15min ~ 90min, is more preferably 45min ~ 60min.For PE, the temperature of forming process is generally 150 ~ 190 DEG C, is preferably 165 DEG C; Molding time is preferably 15min ~ 90min, is more preferably 45min ~ 60min.Specific embodiments of the invention adopt the mode of extruding pelletization to prepare, and length-to-diameter ratio is 25:1; Zone temperatures respectively extruded by forcing machine is 50 ~ 250 DEG C, and extruder temperature can be set to: a district is 170 DEG C ~ 175 DEG C, and 2nd district are 175 DEG C ~ 180 DEG C, and 3rd district are 180 DEG C ~ 185 DEG C, and head temperature is 180 DEG C; Forcing machine revolution is 25 ~ 450 revs/min.
After obtained degradable straw wood-plastic composite material, the present invention carries out performance test to it, wherein adopts the mechanical property of universal testing machine test wood plastic composite.Result shows, wood plastic composite of the present invention in use has the physicochemical property identical with normal wood plastic composite materials and use properties, as low in water-intake rate (water-intake rate < 2%), not easily strain cracking, and Anti-moth-eating goes mouldy; Have that mechanical property is high, light weight, protection against the tide, acid and alkali-resistance, corrosion-resistant and be convenient to the features such as cleaning, can substitute the uses such as log, plastics and aluminium alloy in a lot of field, market application foreground is extensive.
Degradable straw wood-plastic composite material is placed in thermocompressor by the present invention, is to be hot pressed into sheet specimens under the condition of 180 DEG C in temperature, then sample is placed in 70 DEG C of baking ovens and carries out thermal destruction test.Result shows, and through 3 months, sample was degraded, and mechanical strength declines.Show that wood plastic composite of the present invention can carry out being oxidized-biological degradation after reaching work-ing life in physical environment, thus can not to environment.
In order to understand the present invention further, below in conjunction with embodiment, degradable wood plastic composite provided by the invention and preparation method thereof is described particularly.
Embodiment 1
The EBPmas-PE-1501 (purchased from Shandong Ecology Benign Plastics Technology Co., Ltd.) of the HDPE (number-average molecular weight is 100,000) of 60 mass parts, the antioxidant 1010 of 0.5 mass parts and 5 mass parts is mixed, after 10min, obtains compound;
After described compound is mixed with the wood powder (crossing 40 mesh sieves) of 40 mass parts, carry out extruding pelletization through twin screw extruder, obtain degradable wood plastic composite.Wherein, length-to-diameter ratio is 25:1; Zone temperatures respectively extruded by forcing machine is 50 ~ 250 DEG C, and concrete temperature is set to: a district is 170 DEG C ~ 175 DEG C, and 2nd district are 175 DEG C ~ 180 DEG C, and 3rd district are 180 DEG C ~ 185 DEG C, and head temperature is 180 DEG C; Forcing machine revolution is 450 revs/min.
According to method mentioned above, performance test is carried out in the test of obtained wood plastic composite.Through 3 months, sample of the present invention was degraded, and mechanical strength declines, and wherein tensile strength drops to 10.8MPa by 15.8MPa.
Embodiment 2
The EBPmas-PE-1501 (purchased from Shandong Ecology Benign Plastics Technology Co., Ltd.) of the HDPE (number-average molecular weight is 100,000) of 60 mass parts, the antioxidant 1010 of 0.5 mass parts and 10 mass parts is mixed, after 10min, obtains compound;
After described compound is mixed with the wood powder (crossing 40 mesh sieves) of 40 mass parts, carry out extruding pelletization through twin screw extruder, obtain degradable wood plastic composite.Wherein, length-to-diameter ratio is 25:1; Zone temperatures respectively extruded by forcing machine is 50 ~ 250 DEG C, and concrete temperature is set to: a district is 170 DEG C ~ 175 DEG C, and 2nd district are 175 DEG C ~ 180 DEG C, and 3rd district are 180 DEG C ~ 185 DEG C, and head temperature is 180 DEG C; Forcing machine revolution is 450 revs/min.
According to method mentioned above, performance test is carried out in the test of obtained wood plastic composite.Through 3 months, sample of the present invention was degraded, and mechanical strength declines, and wherein tensile strength drops to 7.2MPa by 15.2MPa.
Embodiment 3
The EBPmas-PE-1501 (purchased from Shandong Ecology Benign Plastics Technology Co., Ltd.) of the HDPE (number-average molecular weight is 100,000) of 60 mass parts, the antioxidant 1010 of 0.5 mass parts and 15 mass parts is mixed, after 10min, obtains compound;
After described compound is mixed with the wood powder (crossing 40 mesh sieves) of 40 mass parts, carry out extruding pelletization through twin screw extruder, obtain degradable wood plastic composite.Wherein, length-to-diameter ratio is 25:1; Zone temperatures respectively extruded by forcing machine is 50 ~ 250 DEG C, and concrete temperature is set to: a district is 170 DEG C ~ 175 DEG C, and 2nd district are 175 DEG C ~ 180 DEG C, and 3rd district are 180 DEG C ~ 185 DEG C, and head temperature is 180 DEG C; Forcing machine revolution is 450 revs/min.
According to method mentioned above, performance test is carried out in the test of obtained wood plastic composite.Through 3 months, sample of the present invention was degraded, and mechanical strength declines, and wherein tensile strength drops to 3.5MPa by 14.5MPa.
Comparative example
The antioxidant 1010 of the HDPE (number-average molecular weight is 100,000) of 60 mass parts and 0.5 mass parts is mixed, after 10min, obtains compound;
After described compound is mixed with the wood powder (crossing 40 mesh sieves) of 40 mass parts, carry out extruding pelletization through twin screw extruder, obtain degradable wood plastic composite.Wherein, length-to-diameter ratio is 25:1; Zone temperatures respectively extruded by forcing machine is 50 ~ 250 DEG C, and concrete temperature is set to: a district is 170 DEG C ~ 175 DEG C, and 2nd district are 175 DEG C ~ 180 DEG C, and 3rd district are 180 DEG C ~ 185 DEG C, and head temperature is 180 DEG C; Forcing machine revolution is 450 revs/min.
According to method mentioned above, performance test is carried out in the test of obtained wood plastic composite.Through 3 months, sample of the present invention was not degraded, and wherein tensile strength is 15.5MPa.
As seen from the above embodiment, the present invention with the addition of a certain amount of oxidation-bio-degradable additive, uses oxidation-biodegradation plastic technology, make wood plastic composite have oxidative degradation and biodegradable ability concurrently, and its degradation time is controlled; When carrying out being oxidized-biological degradation in physical environment after wood plastic composite reaches work-ing life, thus can not to environment.Meanwhile, wood plastic composite of the present invention in use has the physicochemical property identical with normal wood plastic composite materials and use properties.
Claims (10)
1. a degradable wood plastic composite, comprising:
Non-degradable plastic matrix, wood fiber powder, oxidation-bio-degradable additive and oxidation inhibitor;
The mass ratio of described non-degradable plastic matrix and wood fiber powder is (90 ~ 20): (10 ~ 80);
The quality of described oxidation-bio-degradable additive accounts for 1% ~ 20% of non-degradable plastic matrix and wood fiber powder total mass;
The quality of described oxidation inhibitor accounts for 0.1% ~ 10% of non-degradable plastic matrix and wood fiber powder total mass.
2. wood plastic composite according to claim 1, is characterized in that, the mass ratio of described non-degradable plastic matrix and wood fiber powder is (80 ~ 30): (20 ~ 70).
3. wood plastic composite according to claim 1, is characterized in that, the quality of described oxidation-bio-degradable additive accounts for 2% ~ 15% of non-degradable plastic matrix and wood fiber powder total mass.
4. wood plastic composite according to claim 1, is characterized in that, the quality of described oxidation inhibitor accounts for 0.5% ~ 5% of non-degradable plastic matrix and wood fiber powder total mass.
5. wood plastic composite according to claim 1, is characterized in that, described non-degradable plastic matrix be selected from polyethylene, polypropylene, polyvinyl chloride and polystyrene one or more.
6. wood plastic composite according to claim 1, is characterized in that, described oxidation-bio-degradable additive comprises nano transition metal inorganics, transition metal salt, poly-basic organic acid and plastic substrate.
7. wood plastic composite according to claim 6, is characterized in that, described oxidation-bio-degradable additive obtains in accordance with the following methods:
Mix in a solvent by transition metal salt and poly-basic organic acid and containing the presoma of transition metal, obtain mixed solution;
After described mixed solution is made inverse micellar solution, carry out successively being incubated, ageing be separated, obtain polynary nanometer particle;
Carry out extruding pelletization by after described polynary nanometer particle and plastic substrate mixing, obtain oxidation-bio-degradable additive.
8. a preparation method for degradable wood plastic composite, comprises the following steps:
After blended to non-degradable plastic matrix, wood fiber powder, oxidation-bio-degradable additive and oxidation inhibitor, carry out forming process, obtain degradable wood plastic composite;
The mass ratio of described non-degradable plastic matrix and wood fiber powder is (90 ~ 20): (10 ~ 80);
The quality of described oxidation-bio-degradable additive accounts for 1% ~ 20% of non-degradable plastic matrix and wood fiber powder total mass;
The quality of described oxidation inhibitor accounts for 0.1% ~ 10% of non-degradable plastic matrix and wood fiber powder total mass.
9. preparation method according to claim 8, is characterized in that, is specially: by non-degradable plastic matrix and oxidation-bio-degradable additive and oxidation inhibitor mixing, obtain compound;
After being mixed with wood fiber powder by described compound, carry out forming process, obtain degradable wood plastic composite.
10. preparation method according to claim 9, is characterized in that, the temperature of described forming process is 150 DEG C ~ 250 DEG C, and the time of described forming process is 10min ~ 1h.
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