CN103819801B - A kind of polyolefin-based wood plastic composite and preparation method thereof - Google Patents
A kind of polyolefin-based wood plastic composite and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a kind of polyolefin-based wood plastic composite and preparation method thereof, the vegetable fibre adopting polyolefine and ethylene-vinyl alcohol copolymer (EVOH) modification is main raw material, adds softening agent, stablizer, lubricant etc. and prepares satisfactory mechanical property, eco-friendly wood plastic composite by melt-mixing method general in plastic working.Wood plastic composite of the present invention can be used for, as general field such as building materials, finishing material, foam material, sheet material, wrapping material, toy, auto parts, having widened the range of application of ethylene-vinyl alcohol copolymer.
Description
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 take vegetable fibre as a kind of type material that main ingredient and thermoplastics are formed by certain method for processing forming compound, it has the dual nature of natural fiber and plastics concurrently, both deficiencies can be made up, the intensity overcoming timber is low uses limitation with large grade of variability, have cheap, mechanical property is good, acid-alkali-corrosive-resisting, the features such as recoverable, timber can be substituted in multiple occasion to use, the contradiction that its development and popularization will effectively alleviate China's oil and forest reserves supply shortage, reduce plastics and the pollution of agricultural wastes burning to environment.
But although development wood plastic composite is significant, its development & application is also faced with many problems.Because plant fibre surface contains a large amount of alcoholic extract hydroxyl groups and phenolic hydroxyl group, 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, when the dispersiveness of both compound tense vegetable fibres in polymeric matrix is not good, easily reunite, both poor compatibility, interface snap-in force is more weak.When material is subject to External Force Acting, stress can not effectively be transmitted in interface, interfacial detachment easily occurs material is destroyed.Therefore, improving the interface compatibility between vegetable fibre and polymkeric substance, is prepare the key issue that wood plastic composite will solve.
Domestic many scholars have carried out large quantifier elimination to the consistency how improving vegetable fibre and polymeric matrix; generally take by the means process vegetable fibre of physics or chemistry or add compatilizer and improve consistency between fiber and matrix; as adopted alkaline purification, acidylate, etherificate vegetable fibre or adding 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 mainly passed through to dissolve the pectin, xylogen etc. in vegetable fibre with alkaline purification vegetable fibre, the contact surface increasing vegetable fibre and polymeric matrix improves interface snap-in force, belongs to physical mechanical interlocking, limited to the raising of product properties; And alkali treatment method process is loaded down with trivial details, the waste liquid of process 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 expensive, limit its application industrially.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 produces serious stimulation to the respiratory tract of operator and eyes, harm environment and operator 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 reacted between macromole, reaction is difficulty comparatively, the not clear and definite experimental fact fully of available data proves that anhydride group and vegetable fibre there occurs chemical action, and the effect therefore between them is the hydrogen bond action of physics or Chemical bond need further Science Explorations; And due to the percentage of grafting of maleic anhydride grafted polymer lower, be generally only 0.4% ~ 1%, therefore will reach processing intent, the maleic anhydride grafted polymer large usage quantity of needs.Therefore graftomer uses as compatilizer and first will solve the low problem of compatilizer percentage of grafting, but there is no good solution at present.In recent years, many scholars are devoted to the research of polyolefine multi-element graft copolymer (as Chinese Patent Application No. 02118793 always, 200510035486.3), to improve the percentage of grafting of compatilizer polar groups, but this method is similar to the production of maleic anhydride grafted polymer.Preparation method and operating procedure more complicated, cost is high, and there is the harm of small molecules grafted monomer and environment healthy to operator equally.
For prior art Problems existing, 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 group that can contain with plant fibre surface and phenolic hydroxyl group produce hydrogen bond action, make itself and vegetable fibre there is good consistency natively; And have good affinity up to the ethylene unit unit of 30-70% molar content and matrix polymer in ethylene-vinyl alcohol copolymer, macromolecular chain between the two can be produced be wound around, therefore the modified method such as common compatilizer, coupling agent above mentioned as an alternative of ethylene-vinyl alcohol copolymer, the consistency between vegetable fibre and polymeric matrix can be improved well, thus give polyolefin-based wood plastic composite good mechanical property.This method of modifying there is no pertinent literature and patent report at present.
The correlative study paper retrieving a large amount of patent documentations and publish, only find that the people such as Zhang Yujun are at " Heilongjiang University's natural science journal " upper (2006,23 (1): 124-127) " preparation of EVOH/ montmorillonite laminated compound material and structural characterization " has been delivered, this research with polyvinyl pyrrolidone modified polynite (MMT) for inorganic phase, take ethylene-vinyl alcohol copolymer as matrix resin, EVOH/ montmorillonite composite material has been prepared 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) delivered on " fabrication & properties of TPS/EVOH Composites ", this research ethylene-vinyl alcohol copolymer and thermoplastic starch is blended prepares starch-base biodegradation material, the degradation property of compound system is controlled by the proportioning controlling ethylene-vinyl alcohol copolymer and thermoplastic starch in compound system, the add-on of ethylene-vinyl alcohol copolymer is between 10-40%, similar 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 the blended material with 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 using the surface-modifying agent of ethylene-vinyl alcohol copolymer as thermoplastic starch.Retrieve 1 section of granted patent about ethylene-vinyl alcohol copolymer based composites (ZL201110189511.9) simultaneously, the patent provides one utilizes 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 carries out surface active modification by adding stearic acid 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, this patentee visible does not recognize the compatible role that ethylene-vinyl alcohol copolymer exists calcium sulfate and W-Gum, and vegetable fibre belongs to the diverse material of two classes in scientific classification in additive calcium sulfate involved by patent ZL201110189511.9 and W-Gum and the application, namely this patent acts on without enlightenment the present invention.The present invention directly utilizes ethylene-vinyl alcohol copolymer as the consistency improved in wood plastic composite between polymeric matrix and vegetable fibre, and this modification theory and method of modifying system the applicant propose 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 obtained has inexpensive nontoxic, the advantage such as environmental friendliness, good 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 be made up of them.
Described plant fiber material comprises the fiber after any one such as cauline leaf, stalk, the shell pulverizing of wood powder, bamboo powder and other Woody plant or their mixture.The median size of its fiber is preferably more than 20 orders, and water content is preferably below 5%.
The ethylene 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 be 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 be 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 ester, N, the ethylene bis-fatty acid amides of N-ethylene bis stearic acid amide or modified with polar, or the mixture be made up of 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 plastics, vegetable fibre, softening agent, stablizer, lubricant and filler etc. and obtain 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 2h under the condition of 80-100 DEG C in temperature.Ethylene-vinyl alcohol copolymer to be ground into after powder dry 8h in 90-92 DEG C of vacuum drying oven.
Said components is first carried out premix by proportioning, and the equipment of use is mixing equipment used in usual plastic working, as high-speed mixer, kneader etc.Suitably can heat depending on material situation during premix, this mixing temperature generally should lower than 100 DEG C.Used by material after premix general rubber plastic blend equipment to carry out melt blending, 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, and can be twin screw extruder, single screw extrusion machine and Banbury mixer etc., rotating speed be 30-60r/min.
Beneficial effect of the present invention is: the vinyl alcohol structural unit in (1) ethylene-vinyl alcohol copolymer can produce good interface cohesion with the alcoholic extract hydroxyl group on vegetable fibre and phenolic hydroxyl group, without the need to separately adding interfacial compatibilizer.If this technology obtains large-scale promotion application, the alternative wood plastic composite method of modifying generally used at present, thus alleviate the environmental pollution brought because producing conventional compatilizer.Because commercialization ethylene-vinyl alcohol copolymer is produced by the modernization large chemical complex with strict environmental practice, this with produce compared with maleic anhydride class graftomer process in general plastic working factory, environmental pollution is little and be convenient to Concetrated control.(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 vinyl alcohol two kinds of structural units is adjustable, and this is that the preparation of of a great variety and that loading level is totally different polymer-based carbon composite material of plant fiber provides choice widely.(3) directly can 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, with environmentally safe in its process vegetable fibre process.Ethylene-vinyl alcohol copolymer is macromole properties-correcting agent, in goods use procedure, there is not pollution and the Problem of Failure such as precipitation, migration.
Embodiment
embodiment 1
Feed composition is by weight: high density polyethylene(HDPE) 100 parts, ethylene-vinyl alcohol copolymer 0.1 part (ethylene molar content is 70%), glycerine 0.5 part, wood powder 10 parts, antioxidant 1076 1 part, antioxidant 330 2 parts, polyethylene wax 1 part, whiteruss 2 parts, 20 parts, calcium carbonate.
By wood powder removal of contamination, pulverizing, sieve, is vacuum-drying 2h under the condition of 80 DEG C in temperature.Simultaneously by ethylene-vinyl alcohol copolymer pulverize after in 92 DEG C of vacuum drying ovens dry 8h.After dried ethylene-vinyl alcohol copolymer powder is mixed with glycerine, with 3000r/min, activation treatment 5min is carried out to dried wood powder in the high mixer of 150 DEG C, obtains 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, regulate double-screw extruder screw rotating speed to be 30r/min, charging opening is followed successively by 160 to the temperature of machine head port mould, 180,183,188,192,198,202 DEG C, after screw mixing, extrude tie rod, namely obtain polyolefin-based wood plastic composite through water-cooled, drying, pelletizing.In the obtained Plastic-wooden composite tray of injection moulding machine (one to three district's temperature is followed successively by: 180,190,200 DEG C), can be used for food grade mess-tin or pallet.
Use the mechanical property of universal testing machine test gained matrix material, tensile strength is 31.79MPa, and modulus in flexure is 3629MPa.
embodiment 2
Feed composition is by weight: polyvinyl chloride 100 parts, ethylene-vinyl alcohol copolymer 3.6 parts (ethylene molar content is 30%), glycerine 18 parts, 60 parts, bamboo powder, composite thermal stabilizer 5 parts, misery 13 ester 5 parts of O-phthalic, tributyl acetylcitrate 5 parts, antioxidant 1010 3 parts, antioxidant 300 4 parts, n-butyl stearate 9 parts, oleylamide 6 parts, silica 10 part.
By bamboo powder removal of contamination, pulverizing, sieve, is vacuum-drying 2h under the condition of 100 DEG C in temperature.Simultaneously by ethylene-vinyl alcohol copolymer pulverize after in 90 DEG C of vacuum drying ovens dry 8h.After being mixed with glycerine by dried ethylene-vinyl alcohol copolymer powder, with 6000r/min, activation treatment 10min is carried out to dried bamboo powder in the high mixer of 190 DEG C, obtain the bamboo powder of surface modification.Then in another high mixer, 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 is added with 4000r/min mixed 10min again.Poured into by batch mixing in the Banbury mixer of 190 DEG C and mix 10min under 60r/min, the 15min that finally at room temperature colds pressing after hot pressing 10min under 10MPa on the vulcanizing press of 190 DEG C obtains wood-plastic composite panel, can be used for top ceiling or floor.
Use the mechanical property of universal testing machine test gained matrix material, tensile strength is 34.86MPa, and modulus in flexure is 4562MPa.
embodiment 3
Feed composition is by weight: polypropylene 100 parts, ethylene-vinyl alcohol copolymer 2.4 parts (ethylene molar content is 44%), glycerine 12 parts, straw 40 parts, antioxidant CA 3 parts, antioxidant 2246 2 parts, glyceryl monostearate 3 parts, organosilane 6 parts, wollastonite 10 parts.
By straw removal of contamination, pulverizing, sieve, is vacuum-drying 2h under the condition of 80 DEG C in temperature.Simultaneously by ethylene-vinyl alcohol copolymer pulverize after in 91 DEG C of vacuum drying ovens dry 8h.After dried ethylene-vinyl alcohol copolymer powder is mixed with glycerine, with 4500r/min, activation treatment 7min is carried out to dried straw in the high mixer of 175 DEG C, obtains 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, regulate double-screw extruder screw rotating speed to be 40r/min, charging opening is followed successively by 163 to the temperature of machine head port mould, and 183,186,191,195,200,204 DEG C, extrude after screw mixing, namely pelletizing obtain modified wood powder.Wood plastics composite tubing is prepared by extruding in batch mixing on a single-screw extruder (temperature in one to seven district is followed successively by: 165,185,188,192,196,201,205 DEG C).
Use the mechanical property of universal testing machine test gained matrix material, tensile strength is 33.15MPa, and modulus in flexure is 4321MPa.
embodiment 4
Feed composition is by weight: ethylene-vinyl acetate copolymer 100 parts, ethylene-vinyl alcohol copolymer 2.0 parts (ethylene molar content is 58%), glycerine 8 parts, litter shell powder 50 parts, 3 parts of antioxidant 3114s, 3 parts of antioxidant 300s, 10 parts, mica, glycerine three hydroxy stearic acid ester 12 parts.
By litter shell powder removal of contamination, pulverizing, sieve, is vacuum-drying 2h under the condition of 80 DEG C in temperature.Simultaneously by ethylene-vinyl alcohol copolymer pulverize after in 92 DEG C of vacuum drying ovens dry 8h.After dried ethylene-vinyl alcohol copolymer powder is mixed with glycerine, with 5000r/min, activation treatment 8min is carried out to dried litter shell powder in the high mixer of 170 DEG C, obtains the litter shell powder of surface modification.Then in another high mixer, add polypropylene, antioxidant 3114, antioxidant 300, glycerine three hydroxy stearic acid ester, mica and modification litter shell powder mixed 5min again.Batch mixing is poured in the Banbury mixer of 170 DEG C and mix 10min under 40r/min, finally the 15min that at room temperature colds pressing after hot pressing 10min under 10MPa on the vulcanizing press of 175 DEG C, mixture is obtained wood-plastic composite panel.
Use the mechanical property of universal testing machine test gained matrix material, tensile strength is 32.85MPa, and modulus in flexure is 4812MPa.
comparative example 1
Feed composition is by weight: ethylene-vinyl acetate copolymer 100 parts, glycerine 8 parts, litter shell powder 50 parts, 3 parts of antioxidant 3114s, 3 parts of antioxidant 300s, 10 parts, mica, glycerine three hydroxy stearic acid ester 12 parts.
By litter shell powder removal of contamination, pulverizing, sieve, is vacuum-drying 2h under the condition of 80 DEG C in temperature.Simultaneously by ethylene-vinyl alcohol copolymer pulverize after in 92 DEG C of vacuum drying ovens dry 8h.Litter shell powder and glycerine are dropped in the high mixer of 170 DEG C successively, obtains modification litter shell powder with discharging after 5000r/min mixing 10min.Then in another high mixer, add polypropylene, antioxidant 3114, antioxidant 300, glycerine three hydroxy stearic acid ester, mica and modification litter shell powder mixed 5min again.Poured into by batch mixing in the Banbury mixer of 170 DEG C and mix 10min under 40r/min, the 15min that finally at room temperature colds pressing after by hot pressing 10min under 10MPa on the vulcanizing press of 175 DEG C, mixture obtains wood-plastic composite panel.
Use the mechanical property of universal testing machine test gained matrix material, tensile strength is 16.35MPa, and modulus in flexure is 1328MPa.
The foregoing is only preferred embodiment of the present invention, all equalizations done 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: polyolefine 100 parts, 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;
Preparation method comprises the following steps:
(1) by vegetable fibre removal of contamination, pulverize, sieve, 80-100 DEG C of vacuum-drying 2h;
(2) by ethylene-vinyl alcohol copolymer dry 8h in 90-92 DEG C of vacuum drying oven;
(3) after being mixed with glycerine by dried ethylene-vinyl alcohol copolymer powder, at 150-190 DEG C, activation treatment 5-10min is carried out to dried vegetable fibre, 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.
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 more than 20 orders, and water content is below 5%.
4. polyolefin-based wood plastic composite according to claim 1, is characterized in that: the ethylene 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, 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 one or more the mixture in the ethylene bis-fatty acid amides of polyethylene wax, oxystearic acid, n-butyl stearate, glyceryl monostearate, oleylamide, silicone oil, silicone, organosilane, whiteruss, glycerine three hydroxy stearic acid ester, N, 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. prepare a method for polyolefin-based wood plastic composite as claimed in claim 1, it is characterized in that: comprise the following steps:
(1) by vegetable fibre removal of contamination, pulverize, sieve, 80-100 DEG C of vacuum-drying 2h;
(2) by ethylene-vinyl alcohol copolymer dry 8h in 90-92 DEG C of vacuum drying oven;
(3) after being mixed with glycerine by dried ethylene-vinyl alcohol copolymer powder, at 150-190 DEG C, activation treatment 5-10min is carried out to dried vegetable fibre, 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.
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