CN103819801A - Polyolefin wood-plastic composite and preparation method thereof - Google Patents

Polyolefin wood-plastic composite and preparation method thereof Download PDF

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CN103819801A
CN103819801A CN201410089582.5A CN201410089582A CN103819801A CN 103819801 A CN103819801 A CN 103819801A CN 201410089582 A CN201410089582 A CN 201410089582A CN 103819801 A CN103819801 A CN 103819801A
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plastic composite
polyolefin
ethylene
antioxidant
vinyl alcohol
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CN103819801B (en
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朱德钦
生瑜
陈星�
生政天
童庆松
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Fujian Normal University
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Fujian Normal University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853Vinylacetate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
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    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
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    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a polyolefin wood-plastic composite and a preparation method thereof. Polyolefin and plant fiber modified by EVOH (ethylene-vinyl alcohol copolymer) are taken as main raw materials, a plasticizer, a stabilizer, a lubricating agent and the like are added, and the environment-friendly wood-plastic composite with excellent mechanical property is prepared with a melt blending method commonly used during plastic processing. The wood-plastic composite can be used in conventional fields such as building materials, decorative materials, foam materials, boards, packaging materials, toys, automobile parts and the like, and the application range of the EVOH is enlarged.

Description

A kind of polyolefin-based wood plastic composite and preparation method thereof
Technical field
The invention belongs to technical field of polymer processing, be specifically related to a kind of polyolefin-based wood plastic composite and preparation method thereof.
Background technology
Wood plastic composite is take vegetable fibre as main ingredient and thermoplastics passes through certain compound a kind of type material forming of method for processing forming, it has the dual nature of natural fiber and plastics concurrently, can make up both deficiencies, overcome low and large grade of variability of the intensity of timber and use limitation, have cheap, mechanical property is good, acid-alkali-corrosive-resisting, the features such as recoverable, can substitute timber in multiple occasion uses, its development and popularization will effectively be alleviated the contradiction of China's oil and forest reserves supply shortage, reduce plastics and agricultural wastes and burn the pollution to environment.
But although development wood plastic composite is significant, its exploitation is also faced with many problems with application.Because a large amount of alcoholic extract hydroxyl groups and phenolic hydroxyl group are contained in vegetable fibre surface, these hydroxyls easily form intermolecular or intramolecular hydrogen bond, have strong polarity and water-absorbent; And thermoplastic polymer surface is generally nonpolar or low-pole, not good when the dispersiveness of both compound tense vegetable fibres in polymeric matrix, easily reunite, both consistencies are poor, interface snap-in force a little less than.In the time that material is subject to External Force Acting, stress can not effectively be transmitted in interface, interface unsticking easily occurs material is destroyed.Therefore, improving the interface compatibility between vegetable fibre and polymkeric substance, is to prepare the key issue that wood plastic composite will solve.
Domestic many scholars have carried out a large amount of research to the consistency that how to improve vegetable fibre and polymeric matrix; generally take process vegetable fibre or add compatilizer and improve the consistency between fiber and matrix by the means of physics or chemistry; as adopt alkaline purification, acidylate, etherificate vegetable fibre or add silane coupling agent, isocyanate coupler, maleic anhydride grafted polymer etc. as compatilizer; to improving the consistency of vegetable fibre and polymeric matrix, but these methods all have some shortcomings part.As being mainly that the contact surface that increases vegetable fibre and polymeric matrix improves interface snap-in force, belongs to physical mechanical interlocking, limited to the raising of product properties by dissolving pectin, the xylogen etc. in vegetable fibre with alkaline purification vegetable fibre; And alkali treatment method process is loaded down with trivial details, the waste liquid of processing can cause serious pollution to environment, general less employing.Coupling agent is the good compatilizer of a class treatment effect, but due to coupling agent price comparison costliness, has limited it in industrial application.Graftomer is a class compatilizer of current most study, wherein general with maleic anhydride grafted polymer.But the operation that the need of production of maleic anhydride grafted polymer is other, and in production process, the volatilization of the small molecules grafted monomer such as maleic anhydride respiratory tract and the eyes to operator produce serious stimulation, and harm environment and operator are healthy.Although use maleic anhydride grafted polymer as the principle of compatilizer be based on maleic anhydride can with alcoholic extract hydroxyl group on vegetable fibre and phenolic hydroxyl group generation esterification, but because the esterification between maleic anhydride grafted polymer and vegetable fibre is to react between macromole, reaction is difficulty comparatively, the not clear and definite experimental fact fully of available data proves that chemical action has occurred for anhydride group and vegetable fibre, and therefore the effect between them is that hydrogen bond action or the Chemical bond of physics need further Science Explorations; And because the percentage of grafting of maleic anhydride grafted polymer is lower, be only generally 0.4% ~ 1%, therefore to reach processing intent, the maleic anhydride grafted polymer large usage quantity needing.Therefore graftomer uses and first will solve the problem that compatilizer percentage of grafting is low as compatilizer, but there is no at present good solution.In recent years, the research that many scholars are devoted to polyolefine multi-element graft copolymer is always (as Chinese Patent Application No. 02118793,200510035486.3), to improve the percentage of grafting of compatilizer Semi-polarity group, but this method is similar to the production of maleic anhydride grafted polymer.Preparation method and operating procedure are more complicated, and cost is high, and have equally the harm of small molecules grafted monomer and environment healthy to operator.
The problem existing for prior art, the present invention adopts commercial ethylene-vinyl alcohol copolymer (EVOH) modified plant fibers.Due to the vinyl alcohol structural unit up to 70-30 % molar content in ethylene-vinyl alcohol copolymer, a large amount of alcoholic extract hydroxyl groups that can contain with vegetable fibre surface and phenolic hydroxyl group produce hydrogen bond action, make natively itself and vegetable fibre have good consistency; And ethene structural unit and matrix polymer up to 30-70% molar content in ethylene-vinyl alcohol copolymer have good affinity, can produce the two macromolecular chain is wound around, therefore the modified method such as common compatilizer, coupling agent that ethylene-vinyl alcohol copolymer is above mentioned as an alternative, can improve well the consistency between vegetable fibre and polymeric matrix, thereby give the mechanical property that polyolefin-based wood plastic composite is good.This method of modifying there is no pertinent literature and patent report at present.
Retrieve a large amount of patent documentations and the correlative study paper of publishing, only find that the people such as Zhang Yujun are at " Heilongjiang University's natural science journal " upper (2006,23 (1): 124-127) delivered " preparation of EVOH/montmorillonite laminated compound material and structural characterization ", this research is take polyvinyl pyrrolidone modified polynite (MMT) as inorganic phase, take ethene-vinyl alcohol copolymer as matrix resin, prepare EVOH/montmorillonite composite material by fusion intercalation, reduce the water absorbability of matrix material, and improve cost performance.The people such as Tang Zhongzhu are at " Journal of Functional Polymers " (2005, 18 (3): 368-372) on, delivered " preparation of TPS/EVOH Composites and performance ", this research is prepared starch-base biodegradation material with ethylene-vinyl alcohol copolymer and thermoplastic starch blend, control the degradation property of compound system by the proportioning of ethylene-vinyl alcohol copolymer and thermoplastic starch in control compound system, the add-on of ethylene-vinyl alcohol copolymer is between 10-40%, similarly research also has the people such as Zhang Meijie in " plastics industry " (2003, 31 (1): 27-29) " the preparation and property research of TPS/ EVOH blend " delivered.In above-mentioned literary composition, be all using ethylene-vinyl alcohol copolymer as with the blended material of thermoplastic starch to improve the degradation property of starch/ethylene-vinyl alcohol copolymer matrix material, in formula, the consumption of expensive ethylene-vinyl alcohol copolymer is large, does not also explicitly point out the surface-modifying agent using ethylene-vinyl alcohol copolymer as thermoplastic starch.Retrieve 1 piece of granted patent about ethylene-vinyl alcohol copolymer based composites (ZL 201110189511.9) simultaneously, this patent provides one to utilize calcium sulfate and W-Gum to manufacture ethylene-vinyl alcohol copolymer based composites and preparation technology thereof, its objective is the cost in order to reduce ethylene-vinyl alcohol copolymer based composites, and give matrix material certain degradation property.This patent is by adding stearic acid to carry out surface active modification to calcium sulfate, to improve calcium sulfate, the consistency of W-Gum and ethylene-vinyl alcohol copolymer, improve the mobility of melt and the surface flatness of matrix material simultaneously, visible this patentee does not recognize the compatible role of ethylene-vinyl alcohol copolymer to calcium sulfate and W-Gum existence, and in the related additive calcium sulfate of patent ZL 201110189511.9 and W-Gum and the application, vegetable fibre belongs to the diverse material of two classes in scientific classification, this patent to the present invention without enlightenment effect.The present invention directly utilizes ethylene-vinyl alcohol copolymer as improving the consistency between polymeric matrix and vegetable fibre in wood plastic composite, and this modification theory and method of modifying are that the applicant proposes first.
Summary of the invention
The object of the present invention is to provide a kind of polyolefin-based wood plastic composite and preparation method thereof, technique is simple, easy to operate, production efficiency is high, production of articles cost is low, and the wood plastic composite obtaining has inexpensive nontoxic, environmental friendliness, the good advantage such as mechanical property and material recoverable, can be used for as fields such as food product pack, toy, building materials, finishing material, foam material, sheet material, auto parts, expand the range of application of ethylene-vinyl alcohol copolymer
For achieving the above object, the present invention adopts following technical scheme:
Composition of raw materials is by weight:
Described polyolefine is that described plastics comprise following thermoplastics: polyethylene, polypropylene, polyvinyl chloride, polystyrene, EVA, or the mixture being made up of them.
Described plant fiber material comprises fiber after any pulverizing such as the cauline leaf, stalk, shell of wood powder, bamboo powder and other Woody plant or their mixture.More than the median size of its fiber is preferably 20 orders, water content is preferably below 5%.
The ethene molar content of described ethylene-vinyl alcohol copolymer is 30-70%.
Described softening agent is misery 13 esters of O-phthalic, misery 14 esters of O-phthalic, diethyl phthalate, tributyl acetylcitrate, clorafin, dibutyl maleate, stearic acid, Zinic stearas, calcium stearate, barium stearate, Octyl adipate or polyurethane plasticizer, or the mixture being made up of them.
Described oxidation inhibitor is antioxidant 330, antioxidant 3114, antioxidant 1076, antioxidant 1010, antioxidant CA, anti-oxidant DLTP, antioxidant 2246, antioxidant 2246-S or antioxidant 300, or the mixture being made up of them.
Described lubricant refers to that described lubricant is polyethylene wax, oxystearic acid, n-butyl stearate, glyceryl monostearate, oleylamide, silicone oil, silicone, organosilane, whiteruss, glycerine three hydroxy stearic acid esters, N, the ethylene bis-fatty acid amides of N-ethylene bis stearic acid amide or modified with polar, or the mixture being formed by them.
Described filler is calcium carbonate, wollastonite, kaolin, clay, mica, silicon-dioxide, glass microballon, graphite, carbon black, talcum powder, titanium dioxide, magnesium hydroxide, aluminium hydroxide, magnesium oxide, aluminum oxide, barium sulfate, zinc oxide, or the mixture of their compositions.
Above-described component is comprised to plastics, vegetable fibre, softening agent, stablizer, lubricant and filler etc. make described wood plastic composite by melt-mixing method general in plastic working.
Concrete grammar be first by plant fiber material removal of contamination, pulverize, sieve, be vacuum-drying 2 h under the condition of 80-100 ℃ in temperature.After being ground into powder, ethylene-vinyl alcohol copolymer in 90-92 ℃ of vacuum drying oven, is dried 8 h.
Said components is first carried out to premix by proportioning, and the equipment of use is mixing equipment used in common plastic working, as high-speed mixer, kneader etc.When premix, can suitably heat depending on material situation, this mixing temperature generally should be lower than 100 ℃.Use general rubber plastic blend equipment to carry out melt blending the material after premix, then obtain wood plastic composite of the present invention through steps such as extruding pelletizations.Blending equipment is the general blending equipment in rubber and plastic processing industry, can be twin screw extruder, single screw extrusion machine and Banbury mixer etc., and rotating speed is 30-60 r/min.
Beneficial effect of the present invention is: the alcoholic extract hydroxyl group that the vinyl alcohol structural unit in (1) ethylene-vinyl alcohol copolymer can be on vegetable fibre and phenolic hydroxyl group produce good interface and be combined, without separately adding interfacial compatibilizer.If this technology obtains large-scale promotion application, the alternative wood plastic composite method of modifying generally using at present, thus alleviate the environmental pollution bringing because producing conventional compatilizer.Because commercialization ethylene-vinyl alcohol copolymer is to be produced by the modernization large chemical complex with strict environmental practice, this is compared with producing maleic anhydride class graftomer process in general plastic working factory, and environmental pollution is little and be convenient to concentrate and administer.(2) ethylene-vinyl alcohol copolymer is of a great variety, vinyl alcohol molar content 30-70 %, and properties-correcting agent choice is large.In ethylene-vinyl alcohol copolymer molecular structure, the ratio of ethene and two kinds of structural units of vinyl alcohol is adjustable, and this provides choice widely for preparation of a great variety and polymer-based carbon composite material of plant fiber that loading level is totally different.(3) can directly process vegetable fibre, easy to operate, technique is simple, and production efficiency is high, and production of articles cost is low.(4) ethylene-vinyl alcohol copolymer itself is nontoxic, processes environmentally safe in vegetable fibre process with it.Ethylene-vinyl alcohol copolymer is macromole properties-correcting agent, in goods use procedure, do not exist separate out, pollution and the Problem of Failure such as migration.
Embodiment
embodiment 1
Feed composition is by weight: 100 parts of high density polyethylene(HDPE)s, 0.1 part of ethylene-vinyl alcohol copolymer (ethene molar content is 70%), 0.5 part of glycerine, 10 parts of wood powders, 1 part of antioxidant 1076,2 parts of antioxidant 330s, 1 part of polyethylene wax, 2 parts of whiterusss, 20 parts, calcium carbonate.
By wood powder removal of contamination, pulverize, sieve, be vacuum-drying 2 h under the condition of 80 ℃ in temperature.After ethylene-vinyl alcohol copolymer being pulverized, in 92 ℃ of vacuum drying ovens, be dried 8 h simultaneously.After dried ethylene-vinyl alcohol copolymer powder is mixed with glycerine, dried wood powder is carried out to activation treatment 5 min with 3000 r/min in the high mixer of 150 ℃, obtain the wood powder of surface modification.Then in another high mixer, add high density polyethylene(HDPE), antioxidant 1076, antioxidant 330, polyethylene wax, whiteruss, modified wood powder and calcium carbonate mixed 5min again.Take out compound, drop in twin screw extruder, regulating double-screw extruder screw rotating speed is 30 r/min, and charging opening is followed successively by 160 to the temperature of machine head port mould, 180,183,188,192,198,202 ℃, after screw mixing, extrude tie rod, obtain polyolefin-based wood plastic composite through water-cooled, dry, pelletizing.Make wood at injection moulding machine (Yi Zhi tri-district's temperature are followed successively by: 180,190,200 ℃) and mould composite pallet, can be used for food grade mess-tin or pallet.
The mechanical property that uses universal testing machine test gained matrix material, tensile strength is 31.79 MPa, modulus in flexure is 3629 MPa.
embodiment 2
Feed composition is by weight: 100 parts of polyvinyl chloride, 3.6 parts of ethylene-vinyl alcohol copolymers (ethene molar content is 30%), 18 parts of glycerine, 60 parts, bamboo powder, 5 parts of composite thermal stabilizers, 5 parts of misery 13 esters of O-phthalic, 5 parts of tributyl acetylcitrates, 3 parts of antioxidant 1010s, 4 parts of antioxidant 300s, 9 parts of n-butyl stearate, 6 parts of oleylamide, 0 part of silica 1.
By bamboo powder removal of contamination, pulverize, sieve, be vacuum-drying 2 h under the condition of 100 ℃ in temperature.After ethylene-vinyl alcohol copolymer being pulverized, in 90 ℃ of vacuum drying ovens, be dried 8 h simultaneously.After dried ethylene-vinyl alcohol copolymer powder is mixed with glycerine, dried bamboo powder is carried out to activation treatment 10 min with 6000 r/min in the high mixer of 190 ℃, obtain the bamboo powder of surface modification.Then in another high mixer, add polyvinyl chloride, composite thermal stabilizer, misery 13 esters of O-phthalic, tributyl acetylcitrate, antioxidant 1010, antioxidant 300, n-butyl stearate, oleylamide, modified bamboo powder and silicon-dioxide with 4000 r/min mixed 10 min again.Batch mixing is poured in the Banbury mixer of 190 ℃ and under 60 r/min, mixed 10 min, 15 min that finally at room temperature cold pressing after hot pressing 10 min under 10 MPa on the vulcanizing press of 190 ℃ make wood-plastic composite panel, can be used for top ceiling or floor.
The mechanical property that uses universal testing machine test gained matrix material, tensile strength is 34.86 MPa, modulus in flexure is 4562MPa.
embodiment 3
Feed composition is by weight: 100 parts of polypropylene, 2.4 parts of ethylene-vinyl alcohol copolymers (ethene molar content is 44%), 12 parts of glycerine, 40 parts of straws, 3 parts of antioxidant CAs, 2 parts of antioxidant 2246s, 3 parts of glyceryl monostearates, 6 parts of organosilanes, 10 parts of wollastonites.
By straw removal of contamination, pulverize, sieve, be vacuum-drying 2 h under the condition of 80 ℃ in temperature.After ethylene-vinyl alcohol copolymer being pulverized, in 91 ℃ of vacuum drying ovens, be dried 8h simultaneously.After dried ethylene-vinyl alcohol copolymer powder is mixed with glycerine, dried straw is carried out to activation treatment 7 min with 4500 r/min in the high mixer of 175 ℃, obtain the straw of surface modification.Then in another high mixer, add polypropylene, antioxidant CA, antioxidant 2246, glyceryl monostearate, organosilane, modification straw and wollastonite mixed 5min again.Take out compound, drop in twin screw extruder, regulating double-screw extruder screw rotating speed is 40 r/min, and charging opening is followed successively by 163,183 to the temperature of machine head port mould, 186,191,195,200,204 ℃, after screw mixing, extrude, pelletizing obtain modified wood powder.Batch mixing is extruded on single screw extrusion machine to the wooden plastic composite pipe of preparation in (temperature in Yi Zhi 7th district is followed successively by: 165,185,188,192,196,201,205 ℃).
The mechanical property that uses universal testing machine test gained matrix material, tensile strength is 33.15 MPa, modulus in flexure is 4321 MPa.
embodiment 4
Feed composition is by weight: 100 parts of ethylene-vinyl acetate copolymers, 2.0 parts of ethylene-vinyl alcohol copolymers (ethene molar content is 58%), 8 parts of glycerine, 50 parts of litter shell powders, 3 parts of antioxidant 3114s, 3 parts of antioxidant 300s, 10 parts, mica, 12 parts of glycerine three hydroxy stearic acid esters.
By litter shell powder removal of contamination, pulverize, sieve, be vacuum-drying 2 h under the condition of 80 ℃ in temperature.After ethylene-vinyl alcohol copolymer being pulverized, in 92 ℃ of vacuum drying ovens, be dried 8h simultaneously.After dried ethylene-vinyl alcohol copolymer powder is mixed with glycerine, dried litter shell powder is carried out to activation treatment 8 min with 5000 r/min in the high mixer of 170 ℃, obtain the litter shell powder of surface modification.Then in another high mixer, add polypropylene, antioxidant 3114, antioxidant 300, glycerine three hydroxy stearic acid esters, mica and modification litter shell powder mixed 5min again.Batch mixing is poured in the Banbury mixer of 170 ℃ and under 40 r/min, mixed 10 min, finally 15 min that at room temperature cold pressing after hot pressing 10 min under 10 MPa on the vulcanizing press of 175 ℃, mixture are made to wood-plastic composite panel.
The mechanical property that uses universal testing machine test gained matrix material, tensile strength is 32.85 MPa, modulus in flexure is 4812MPa.
comparative example 1
Feed composition is by weight: 100 parts of ethylene-vinyl acetate copolymers, 8 parts of glycerine, 50 parts of litter shell powders, 3 parts of antioxidant 3114s, 3 parts of antioxidant 300s, 10 parts, mica, 12 parts of glycerine three hydroxy stearic acid esters.
By litter shell powder removal of contamination, pulverize, sieve, be vacuum-drying 2 h under the condition of 80 ℃ in temperature.After ethylene-vinyl alcohol copolymer being pulverized, in 92 ℃ of vacuum drying ovens, be dried 8h simultaneously.Litter shell powder and glycerine are dropped into successively in the high mixer of 170 ℃, mix 10 min with 5000 r/min after discharging make modification litter shell powder.Then in another high mixer, add polypropylene, antioxidant 3114, antioxidant 300, glycerine three hydroxy stearic acid esters, mica and modification litter shell powder mixed 5min again.Batch mixing is poured in the Banbury mixer of 170 ℃ and under 40 r/min, mixed 10 min, finally 15 min that at room temperature cold pressing after hot pressing 10 min under 10 MPa on the vulcanizing press of 175 ℃, mixture are being made to wood-plastic composite panel.
The mechanical property that uses universal testing machine test gained matrix material, tensile strength is 16.35 MPa, modulus in flexure is 1328MPa.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (9)

1. a polyolefin-based wood plastic composite, is characterized in that: described matrix material is prepared from by the raw material of following parts by weight: 100 parts of polyolefine, ethylene-vinyl alcohol copolymer 0.1-3.6 part, glycerine 0.5-18 part, vegetable fibre 10-60 part, softening agent 0-10 part, oxidation inhibitor 3-7 part, lubricant 3-15 part, filler 10-20 part.
2. polyolefin-based wood plastic composite according to claim 1, is characterized in that: described polyolefine is one or more the mixture in polyethylene, polypropylene, polyvinyl chloride, polystyrene, EVA.
3. polyolefin-based wood plastic composite according to claim 1, it is characterized in that: described vegetable fibre is one or more in timber, bamboo, rattan, stalk, rice husk, fiber crops, reed, coconut husk, Pericarppium arachidis hypogaeae, the median size of its fiber is that more than 20 orders water content is below 5%.
4. polyolefin-based wood plastic composite according to claim 1, is characterized in that: the ethene molar content of described ethylene-vinyl alcohol copolymer is 30-70%.
5. polyolefin-based wood plastic composite according to claim 1, is characterized in that: described softening agent is one or more the mixture in misery 13 esters of O-phthalic, misery 14 esters of O-phthalic, diethyl phthalate, tributyl acetylcitrate, clorafin, dibutyl maleate, stearic acid, Zinic stearas, calcium stearate, barium stearate, Octyl adipate, polyurethane plasticizer.
6. polyolefin-based wood plastic composite according to claim 1, is characterized in that: described oxidation inhibitor is one or more the mixture in antioxidant 330, antioxidant 3114, antioxidant 1076, antioxidant 1010, antioxidant CA, anti-oxidant DLTP, antioxidant 2246, antioxidant 2246-S, antioxidant 300.
7. polyolefin-based wood plastic composite according to claim 1, it is characterized in that: described lubricant is polyethylene wax, oxystearic acid, n-butyl stearate, glyceryl monostearate, oleylamide, silicone oil, silicone, organosilane, whiteruss, glycerine three hydroxy stearic acid esters, N, the mixture of one or more in the ethylene bis-fatty acid amides of N-ethylene bis stearic acid amide, modified with polar.
8. polyolefin-based wood plastic composite according to claim 1, is characterized in that: described filler is one or more the mixture in calcium carbonate, wollastonite, kaolin, clay, mica, silicon-dioxide, glass microballon, graphite, carbon black, talcum powder, titanium dioxide, magnesium hydroxide, aluminium hydroxide, magnesium oxide, aluminum oxide, barium sulfate, zinc oxide.
9. a method of preparing polyolefin-based wood plastic composite as claimed in claim 1, is characterized in that: comprise the following steps:
(1) by vegetable fibre removal of contamination, pulverize, sieve, 80-100 ℃ of vacuum-drying 2 h;
(2) by ethylene-vinyl alcohol copolymer dry 8 h in 90-92 ℃ of vacuum drying oven;
(3) after dried ethylene-vinyl alcohol copolymer powder is mixed with glycerine, at 150-190 ℃, dried vegetable fibre is carried out to activation treatment 5-10 min, obtain the vegetable fibre of surface modification;
(4) vegetable fibre of polyolefine, surface modification, softening agent, oxidation inhibitor, lubricant and filler are mixed, by mixing, extrude, granulation obtains the described polyolefin-based wood plastic composite through ethylene-vinyl alcohol copolymer modification.
CN201410089582.5A 2014-03-13 2014-03-13 A kind of polyolefin-based wood plastic composite and preparation method thereof Active CN103819801B (en)

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CN104292700A (en) * 2014-10-22 2015-01-21 安徽恒晶电缆集团有限公司 High-strength high-toughness modified polyvinyl chloride insulating cable material
CN104311948A (en) * 2014-10-10 2015-01-28 周伟 Formula and production process of PE sythetic-wood decoration surface plate
CN104629396A (en) * 2015-01-14 2015-05-20 安徽耐科挤出科技股份有限公司 High-weather-resistance environment-friendly wood-plastic composite material and preparation method thereof
CN104629395A (en) * 2015-01-14 2015-05-20 安徽耐科挤出科技股份有限公司 High-toughness environment-friendly wood-plastic composite material and preparation method thereof
CN104910641A (en) * 2015-06-30 2015-09-16 江苏旭华圣洛迪建材有限公司 Anti-stretching anti-bending wood-plastic composite material and preparation method thereof
CN105062108A (en) * 2015-07-17 2015-11-18 安徽万兴实业有限公司 Novel microspherical wood-plastic composite
CN105086485A (en) * 2015-08-18 2015-11-25 九江学院 Multi-component composite material of environmental compatible polyester and plants and preparation method of multi-component composite material
CN105482343A (en) * 2015-12-29 2016-04-13 东莞市汉维科技股份有限公司 Plant fiber powder surface treatment aid and preparation method thereof
CN105694230A (en) * 2016-04-25 2016-06-22 华东理工大学 Environment-friendly plastifying biomass composite and preparation method thereof
CN106117918A (en) * 2016-08-31 2016-11-16 浙江省现代纺织工业研究院 A kind of high-barrier aging resistance particulate polyvinyl chloride and the preparation method of thin film
CN106221000A (en) * 2016-07-28 2016-12-14 陈林美 A kind of high intensity tear-resistant polypropylene film formula
CN106336557A (en) * 2016-09-29 2017-01-18 芜湖市三山区绿色食品产业协会 High-toughness polyethylene foamed packaging film and preparation method thereof
CN106380768A (en) * 2016-08-29 2017-02-08 桂林舒康建材有限公司 Wood-plastic composite material
CN106497118A (en) * 2016-11-17 2017-03-15 过冬 A kind of wood plastic composite, its preparation method and the dieplate being made up of the composite
CN107353525A (en) * 2017-07-10 2017-11-17 芜湖扬展新材料科技服务有限公司 A kind of preparation method of modified polystyrene composite material
CN107474321A (en) * 2017-10-18 2017-12-15 桐城市桐佳装饰有限公司 A kind of degradable decoration material and preparation method thereof
CN107641244A (en) * 2016-07-20 2018-01-30 丹阳市飞利健身器材有限公司 A kind of hardware plastic
CN108101418A (en) * 2018-01-26 2018-06-01 南阳理工学院 A kind of environmental-friendly construction material
CN108102255A (en) * 2018-01-08 2018-06-01 安徽以诺木塑板材科技有限公司 A kind of flame retardant type PVC wood plastic plate and preparation method thereof
JP2018104625A (en) * 2016-12-28 2018-07-05 日本合成化学工業株式会社 Resin composition and melt-molded article prepared therewith, and multilayered structure
CN108530732A (en) * 2018-04-27 2018-09-14 陕西杨凌陕特农业发展有限公司 A kind of plastic products and its preparation process for food packaging
CN109021398A (en) * 2018-08-21 2018-12-18 苏州谦合诚智能科技有限公司 A kind of high-toughness high-strength polypropylene plastics and preparation method thereof
CN109485976A (en) * 2018-11-21 2019-03-19 湖北彩砼新材料有限公司 A kind of super-hydrophobic sheet material of low density polyethylene (LDPE) and preparation method thereof
CN109571915A (en) * 2018-11-19 2019-04-05 苏州市胜佳吸塑有限公司 A kind of processing technology of new energy car battery pallet
CN110343336A (en) * 2019-05-29 2019-10-18 贵州省材料产业技术研究院 A kind of great surface quality polypropylene micro foaming composite material and preparation method thereof
CN110358151A (en) * 2019-07-17 2019-10-22 安吉艾格赛思生物科技有限公司 A kind of bamboo and wood waste biomass cellulose method of comprehensive utilization
CN111349281A (en) * 2020-04-22 2020-06-30 广东联塑科技实业有限公司 Oxygen-barrier PE-RT heating pipe and preparation method thereof

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CN104311948A (en) * 2014-10-10 2015-01-28 周伟 Formula and production process of PE sythetic-wood decoration surface plate
CN104292700A (en) * 2014-10-22 2015-01-21 安徽恒晶电缆集团有限公司 High-strength high-toughness modified polyvinyl chloride insulating cable material
CN104629396A (en) * 2015-01-14 2015-05-20 安徽耐科挤出科技股份有限公司 High-weather-resistance environment-friendly wood-plastic composite material and preparation method thereof
CN104629395A (en) * 2015-01-14 2015-05-20 安徽耐科挤出科技股份有限公司 High-toughness environment-friendly wood-plastic composite material and preparation method thereof
CN104910641A (en) * 2015-06-30 2015-09-16 江苏旭华圣洛迪建材有限公司 Anti-stretching anti-bending wood-plastic composite material and preparation method thereof
CN105062108A (en) * 2015-07-17 2015-11-18 安徽万兴实业有限公司 Novel microspherical wood-plastic composite
CN105062108B (en) * 2015-07-17 2018-07-06 安徽万兴实业有限公司 A kind of microballon wood plastic composite
CN105086485A (en) * 2015-08-18 2015-11-25 九江学院 Multi-component composite material of environmental compatible polyester and plants and preparation method of multi-component composite material
CN105086485B (en) * 2015-08-18 2019-01-01 九江学院 A kind of Environmental compatibility polyester and the multi-element composite material of plant and preparation method thereof
CN105482343A (en) * 2015-12-29 2016-04-13 东莞市汉维科技股份有限公司 Plant fiber powder surface treatment aid and preparation method thereof
CN105694230A (en) * 2016-04-25 2016-06-22 华东理工大学 Environment-friendly plastifying biomass composite and preparation method thereof
CN107641244A (en) * 2016-07-20 2018-01-30 丹阳市飞利健身器材有限公司 A kind of hardware plastic
CN106221000A (en) * 2016-07-28 2016-12-14 陈林美 A kind of high intensity tear-resistant polypropylene film formula
CN106380768A (en) * 2016-08-29 2017-02-08 桂林舒康建材有限公司 Wood-plastic composite material
CN106117918A (en) * 2016-08-31 2016-11-16 浙江省现代纺织工业研究院 A kind of high-barrier aging resistance particulate polyvinyl chloride and the preparation method of thin film
CN106336557A (en) * 2016-09-29 2017-01-18 芜湖市三山区绿色食品产业协会 High-toughness polyethylene foamed packaging film and preparation method thereof
CN106497118A (en) * 2016-11-17 2017-03-15 过冬 A kind of wood plastic composite, its preparation method and the dieplate being made up of the composite
CN106497118B (en) * 2016-11-17 2019-05-14 过冬 A kind of wood plastic composite, preparation method and the profiled sheeting made of the composite material
JP2018104625A (en) * 2016-12-28 2018-07-05 日本合成化学工業株式会社 Resin composition and melt-molded article prepared therewith, and multilayered structure
CN107353525A (en) * 2017-07-10 2017-11-17 芜湖扬展新材料科技服务有限公司 A kind of preparation method of modified polystyrene composite material
CN107474321A (en) * 2017-10-18 2017-12-15 桐城市桐佳装饰有限公司 A kind of degradable decoration material and preparation method thereof
CN108102255A (en) * 2018-01-08 2018-06-01 安徽以诺木塑板材科技有限公司 A kind of flame retardant type PVC wood plastic plate and preparation method thereof
CN108101418A (en) * 2018-01-26 2018-06-01 南阳理工学院 A kind of environmental-friendly construction material
CN108530732A (en) * 2018-04-27 2018-09-14 陕西杨凌陕特农业发展有限公司 A kind of plastic products and its preparation process for food packaging
CN109021398A (en) * 2018-08-21 2018-12-18 苏州谦合诚智能科技有限公司 A kind of high-toughness high-strength polypropylene plastics and preparation method thereof
CN109571915A (en) * 2018-11-19 2019-04-05 苏州市胜佳吸塑有限公司 A kind of processing technology of new energy car battery pallet
CN109485976A (en) * 2018-11-21 2019-03-19 湖北彩砼新材料有限公司 A kind of super-hydrophobic sheet material of low density polyethylene (LDPE) and preparation method thereof
CN110343336A (en) * 2019-05-29 2019-10-18 贵州省材料产业技术研究院 A kind of great surface quality polypropylene micro foaming composite material and preparation method thereof
CN110358151A (en) * 2019-07-17 2019-10-22 安吉艾格赛思生物科技有限公司 A kind of bamboo and wood waste biomass cellulose method of comprehensive utilization
CN111349281A (en) * 2020-04-22 2020-06-30 广东联塑科技实业有限公司 Oxygen-barrier PE-RT heating pipe and preparation method thereof

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