CN107118527B - A method of preparing high water vapor barrier biodegradable composite - Google Patents

A method of preparing high water vapor barrier biodegradable composite Download PDF

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CN107118527B
CN107118527B CN201710402582.XA CN201710402582A CN107118527B CN 107118527 B CN107118527 B CN 107118527B CN 201710402582 A CN201710402582 A CN 201710402582A CN 107118527 B CN107118527 B CN 107118527B
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biodegradable
vapor
composite
composite material
dispersed phase
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CN107118527A (en
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陈蓉
韩艾纯
郭少云
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Sichuan University
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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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Mechanical Engineering (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention is a kind of method for preparing high water vapor barrier biodegradable composite, it is to the effect that using Biodegradable high molecular as matrix, hydrophobic biological degrades ester type compound as dispersed phase, matrix and dispersed phase are subjected to melting mixing and regulate and control morphosis of the biodegradable ester type compound in Biodegradable high molecular matrix, and using its effective influence for compounding polarity decrease vapor on the one hand reducing composite material to composite material and vapor is blocked in the diffusion path of composite material surface, on the other hand increase vapor in the diffusion path of composite inner, to obtain high vapor water barriers performance, and stablize its vapor water barriers performance to ambient humidity.This method is a kind of continuous production process, simple process, and the product quality indicator between different batches is stablized, can large-scale industrial production, there is wide industrialization and market prospects, composite theory research and in terms of be of great significance.

Description

A method of preparing high water vapor barrier biodegradable composite
Technical field
The present invention relates to a kind of preparation methods of high water vapor barrier biodegradable composite, in particular relate to And a kind of prepare that fully biodegradable, melt-processable, good mechanical performance, vapor water barriers performance be excellent and its barrier property It can not be related to composite technology neck with the method for the high water vapor barrier biodegradable composite that ambient humidity changes Domain.
Background technique
Biodegradated polymer materal is a kind of renewable resource from a wealth of sources, there is good biocompatibility, certainly Being easy to degrade in right environment will not pollute, it has also become substitute the preferred of conventional petroleum base plastics, answer in terms of barrier material With extensive.But it is sensitive to vapor that some biodegradated polymer materals such as natural macromolecular material contains hydroxyl and carboxyl etc. Polar group, and synthesizing high molecular material its strand, often there is flexibility vapor to be made to be easy to spread wherein, so it is biological The general vapor water barriers performance of degraded macromolecular material is poor and its vapor water barriers performance can substantially drop under high humidity environment It is low, it is limited in the application in the fields such as food packaging and electron device package.It improves its vapor water barriers performance and increases it Vapor water barriers performance is just particularly important the stability of humidity.
The method that tradition preparation has the composite material of high water vapor barrier property is mainly to regulate and control the diffusion of osmoticum Path is modified etc. to reduce vapor permeability material.Christian Aulin et al. utilizes solution casting method will Nanofiber fiber element is added in 5% high-specific surface area vermiculite, and vapor permeability is by 3.3 ngm/m2SKPa is reduced to 1.0 ng·m/m2SKPa, barrier property improve 70% [1].Quanling Yang et al. utilizes alkyl ketene dimerization Liquid solution, which carries out surface modification to alkali/urea regenerated cellulose, improves the hydrophobicity of material surface, vapor permeability by 10.4 g·μm/m2DayKPa is reduced to 7.1 g μm/m2DayKPa, barrier property improve 33% [2].These Although method can be improved the barrier property of material, but inorganic filler is often difficult to reach fine dispersion and proposes material block performance High limited, in addition the method can not improve Biodegradable material vapor water barriers performance to the stability of humidity: Christian The vapor permeability of the composite material of the preparations such as Aulin rises about 30 times [1] when humidity increases to 80%, and Quanling The modified cellulose film of the preparations such as Yang vapor water barriers performance after relative humidity increases to 80% has dropped 3 orders of magnitude [2]。
Separately there is scholar using being modified to material to improve vapor water barriers performance.Jong-Whan Rhim et al. is utilized The higher polylactic acid of hydrophobicity is introduced in the high agar of solution-cast normal direction hydrophily/carragheen blend, so that the water of material Vapour permeability is by 100 E-11 gm/m2SPa is reduced to 5 E-11 gm/m2SPa, barrier property improve 95%[3].The good modified beeswaxes of hydrophobicity are coated on carbon paper and are prepared for beeswax-carbon paper composite wood by Dan Zhang etc. Material, the experimental results showed that beeswax-carbon paper hydrophobicity is greatly improved, beeswax coated weight is 23g/m2Beeswax-manifolding The moisture-vapor transmission of paper only accounts for uncoated 8%, i.e. vapor water barriers performance improves 92% [4].Federico Carosio Et al. using solution coating by lyophobic dust Nafio be coated in polylactic acid surface, make the vapor permeability of composite material by 160 g·mm/m2Dayatm is reduced to 50gmm/m2Dayatm, barrier property improve 70%, while vapor Barrier property is improved [5] to the stability of humidity.
Although the research of lyophobic dust introduced above can be avoided the aggregation of filler and effectively improve composite material to water The obstructing capacity of steam simultaneously improves barrier property to the stability of humidity, but preparation method is solwution method, preparation process Complexity, solvent remove difficult, it is difficult to continuous large-scale production.To solve this problem, it is prepared to utilization method for melt processing Biodegradable composite with high water vapor barrier property, and make its barrier property that there is good humidity stability, The selection of Biodegradable high molecular matrix and hydrophobic dispersion phase and function compounding are crucial.How Biodegradable high molecular is carried out The effective compounding of matrix and hydrophobic dispersion phase during melt-processed, and composite structure form is controlled to be had The biodegradable composite of high water vapor barrier property is problem in the urgent need to address at this stage.
Bibliography
[1]Aulin C, Salazar-Alvarez G, Lindstrom T. High strength, flexible and transparent nanofibrillated cellulose-nanoclay biohybrid films with tunable oxygen and water vapor permeability, Nanoscale, 2012, 4: 6622-6628.
[2]Yang Q, Saito T, Isogai A. Facile fabrication of transparent cellulose films with high water repellency and gas barrier properties, Cellulose, 2012, 19(6):1913-21.
[3]Jong-Whan Rhim. Effect of PLA lamination on performance characteristics of agar/κ-carrageenan/clay bio-nanocomposite film, Food Research International, 2013, 51: 714–722.
[4]Dan Zhang, and Huining Xiao. Dual-Functional Beeswaxes on Enhancing Antimicrobial Activity and Water Vapor Barrier Property of Paper, ACS Appl. Mater. Interfaces, 2013, 5: 3464−3468.
[5]Federico Carosio, Samuele Colonna, Alberto Fina, Gaulthier Rydzek, Joseph Hemmerle, Loïc Jierry, Pierre Schaaf, and Fouzia Boulmedais. Efficient Gas and Water Vapor Barrier Properties of Thin Poly(lactic acid) Packaging Films: Functionalization with Moisture Resistant Nafion and Clay Multilayers, Chem. Mater, 2014, 26: 5459−5466。
Summary of the invention
It is poor to vapor water barriers performance for the biodegradable barrier material of tradition, under high humidity environment barrier property The shortcomings that failure and existing solwution method prepare the deficiency of vapor water barriers composite material, and the purpose of the present invention is directed to one kind Melt blending prepare fully biodegradable, can be continuously produced, good mechanical performance, vapor water barriers performance are excellent and it is hindered For separating performance not with the method for the high water vapor barrier biodegradable composite of ambient humidity variation, this method passes through biology drop Macromolecule matrix and hydrophobic dispersion are solved mutually in the effective of effective compounding of melt-processed process and composite structure form Regulation, realizes the raising of material vapor water barriers performance in solvent-free simple process, and realizes high water vapor barrier property The characteristics of having both with excellent mechanical performances.This method have simultaneously in processing and use process it is harmless to human body and ecological environment, It can be continuously produced, process is easy, quality is stable, the advantages of being suitable for large-scale industrial production.
Basic principle of the invention is that it is right as hydroxyl, carboxyl isopolarity group to contain class in view of biodegradation material Vapor water barriers performance is poor, and barrier property fails under high humidity environment, if a kind of and Biodegradable high molecular can be selected Matrix compatibility preferably, melt-processable, with the material compared with strong-hydrophobicity be added to Biodegradable high molecular as dispersed phase It,, can be in composite wood on the one hand by the morphosis of regulation composite material using effective compounding of matrix and dispersed phase in matrix Material is internal to form more water vapor diffusion paths, extends vapor substantially by the time of composite material, to reduce water Steam diffusion coefficient；On the other hand the polarity of composite material can be reduced, composite material hydrophobicity and its pole with hydrone are increased Property it is poor, so that the stronger vapor of polarity is difficult to penetrate into the weaker composite inner of polarity, and then significantly reduce vapor pair The swelling action of composite material stablizes composite material property under different humidity environment.Thus it can be obtained with good water The biodegradated polymer materal of vapor barrier performance, barrier property have good humidity stability.The present invention is from this point It sets out, is dedicated to improving the hydrophobicity of blend in the selection of dispersed phase, and increase vapor in the expansion of composite inner Path is dissipated, the permeability of vapor is thus reduced and vapor water barriers performance is kept not change with ambient humidity.Specifically, originally Invention is to use Biodegradable high molecular for matrix, selects melt-processable and has hydrophobic biodegradable esters chemical combination Object regulates and controls the hydrophobicity of blend as dispersed phase, obtains with the composite material compared with high hydrophobicity；And pass through melt blending Method regulate and control dispersity and appearance structure of the biodegradable dispersed phase in Biodegradable high molecular matrix, make to give birth to Object degradation dispersed phase is evenly distributed in Biodegradable high-molecular matrix, on the one hand disperses biodegradable point in the base Dephasing increases the diffusion path of vapor in the base, reduces water vapor diffusion coefficient；On the other hand composite material is improved Surface hydrophobic, vapor is difficult to enter composite inner, reduces vapor to the swelling action of material, to obtain Vapor water barriers performance is excellent and its barrier property does not obstruct biodegradable composite wood with the high water vapor of ambient humidity variation Material.And there is good molecule since biodegradable dispersed phase and Biodegradable high molecular matrix are hydrocarbon oxygen compound Between affinity, the mode of melt blending can regulate and control biodegradable ester type compound in Biodegradable high molecular matrix point Bulk state and pattern are evenly distributed in it in Biodegradable high-molecular matrix, to make Biodegradable high molecular matrix Material is continuous phase, and composite materials property is still maintained.
The present invention is based on above-mentioned principle, realize that technical solution used by foregoing invention purpose is: the present invention is with biology drop Solution macromolecule is matrix, and hydrophobic biological is degraded ester type compound as dispersed phase, first carried out using high mixed or melting mixing technique Premix, remelted plasticizing forming, it is characterised in that:
(1) the Biodegradable high molecular matrix selects melt processing temperature between 80~250 DEG C, the model of hydrophilic contact angle It encloses for the water-insoluble Biodegradable high molecular between 50 °~90 ° such as polycaprolactone, polylactic acid, poly-succinic fourth diester, poly- hydroxyl One of base aliphatic ester, hydroxybutyrate-hydroxyvalerate copolymer, ethyl cellulose and cellulose acetate；
(2) the hydrophobic biological degradation ester type compound is melt processing temperature between 80~250 DEG C, hydrophilic contact Water-insoluble biodegrade glycerin monostearate, glyceryl tristearate, ethylene glycol list of the angle between 90 °~150 ° are stearic Acid esters, glyceryl monolaurate, laurin, single nutmeg acid glyceride, three nutmeg acid glycerides, tripalmitin One of；
(3) Biodegradable high molecular is compared at the hydrophilic contact angle of the degradation of hydrophobic biological selected in system ester type compound High 20 ° of hydrophilic contact angle of matrix or more.
The hydrophilic contact angle of the hydrophobic biological degradation ester type compound compounded in above-mentioned technical proposal should be than corresponding High 20 ° of Biodegradable high molecular matrix or more, using effective compounding of matrix and dispersed phase, on the one hand pass through regulation composite material Morphosis, can composite inner formed increase water vapor diffusion path, make vapor by composite material when Between substantially extend, reduce water vapor diffusion coefficient；On the other hand the polarity of composite material can be reduced, composite material hydrophobicity is increased And its it is poor with the polarity of hydrone, make the stronger vapor of polarity be difficult to penetrate into the weaker composite inner of polarity, in turn Vapor is significantly reduced to the swelling action of composite material, stablizes composite material property under different humidity environment.Thus it is It can get the biodegradated polymer materal with good vapor water barriers performance, and its barrier property has good humidity steady It is qualitative.And this kind of hydrophobic biological degradation ester type compound and Biodegradable high molecular matrix are respectively the carbon of short chain and long-chain Oxyhydroxide has good intermolecular affinity, so hydrophobic biological degradation ester type compound and biodegrade are high The compatibility of the composite material of molecular matrix preparation is good；And since the mode of melt blending can regulate and control biodegradable ester Dispersity and pattern of the class compound in Biodegradable high molecular matrix, while biodegradated polymer materal is continuous Phase, composite materials property difference compared with Biodegradable high molecular matrix are little.It thus can be by biodegradable high The selection and compounding of molecular matrix and hydrophobic biological degradation ester type compound regulate and control hydrophobicity using the method for melt-processed Dispersed phase is evenly distributed in biodegradable matrix, obtains the Gao Shui for having both excellent vapor water barriers performance, mechanical property Vapor barrier biodegradable composite.This novel method for preparing high water vapor barrier biodegradable composite adds Work process is easy, quality is stable and is suitable for large-scale industrial production, can fundamentally solve molten to avoid the use of solvent The problems such as agent is difficult to handle, and pollutes environment.
Height in above-mentioned technical proposal is mixed or melting mixing technique refers to Biodegradable high molecular matrix and hydrophobic biological The mixing that degradation ester type compound dispersed phase carries out in high mixer.
Height in above-mentioned technical proposal is mixed or melting mixing technique refers to Biodegradable high molecular matrix and hydrophobic biological The melting mixing and granulation process that degradation ester type compound dispersed phase carries out in an extruder, wherein feed opening, conveying section, melting Section, homogenizing zone, mouth mold processing temperature be respectively 40~200 DEG C, 80~250 DEG C, 80~250 DEG C, 80~250 DEG C, 70~ 250℃；And by the material after fusion plastification be placed in corresponding mould through vulcanizing press 80~250 DEG C of temperature, pressure 6~ Hot pressing under conditions of 15 MPa is cooled and shaped.
Fusion plastification molding in above-mentioned technical proposal refers to Biodegradable high molecular matrix, hydrophobic biological degradation ester Class compound dispersed phase carries out melting mixing in an extruder, and obtains the high water vapor of required size by different shape mouth mold Obstruct biodegradable composite, wherein feed opening, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 40 ~200 DEG C, 80~250 DEG C, 80~250 DEG C, 80~250 DEG C, 70~250 DEG C.
Fusion plastification molding in above-mentioned technical proposal refers to Biodegradable high molecular matrix, hydrophobic biological degradation ester Class compound dispersed phase carries out fusion plastification in mixer, and processing temperature is 80~250 DEG C, and rotor speed is 15~ 60rpm, fusion time are 3~12min；And the material after fusion plastification is placed in corresponding mould, exist through vulcanizing press It is hot-forming and cooling under conditions of 80~250 DEG C of temperature, 6~15 MPa of pressure.
Fusion plastification molding in above-mentioned technical proposal is that Biodegradable high molecular matrix and hydrophobic biological are degraded Ester type compound melting mixing directly in extruder or mixer, then passes through mouth mold of different shapes or vulcanizing press It is shaped to various sizes of biodegradable composite, such melting mixing and forming process can quickly and easily serializations Produce the adjustable height of dispersion and morphosis of good mechanical performance, dispersed phase in Biodegradable high molecular matrix Vapor water barriers biodegradable polymer.Compared with the solution manufacturing method generally used, dispersed phase morphology structure tune Control is simple, and composite material high production efficiency, product size are easy to control, and are suitable for preparing various sizes of composite material.
The different composite materials that above-mentioned fusion plastification moulding process obtains, as with high water vapor barrier property Biodegradable composite.
The present invention with the solvent method of the prior art prepare high water vapor barrier biodegradable composite method compared with, Sum up have the advantages that it is following prominent:
1, the present invention chooses the hydrophobic biological degradation ester type compound of energy melt-processed, by itself and Biodegradable high molecular Material is compounded, and the composite material of high water vapor barrier is prepared using melt-processed, used melt blending can be simple Regulate and control dispersity and morphosis of the hydrophobic biological degradation ester type compound in Biodegradable high molecular matrix easyly, Vapor is designed in the diffusion path of composite inner and then improves composite material vapor water barriers performance.
2, the introducing of hydrophobic biological degradation ester type compound can significantly improve the hydrophobicity of composite material, reduce water and steam Air infiltration penetrates into the ability of composite material, can be effectively reduced the vapor permeability of biological degradable composite material, significantly reduces water Steam makes composite material all have good water vapor barrier property under different humidity environment the swelling action of composite material Can, while having both excellent mechanical property.
3, the component part biodegrade of novel high water vapor proposed by the invention barrier biodegradable composite Macromolecule matrix and hydrophobic biological degradation ester type compound dispersed phase are the good degradation materials of biocompatibility, to people Body nonhazardous effect, property are stablized, harmful to human body and environment with using that will not decompose or discharge in temperature range processing Gas or substance are to human body and environmental-friendly composite material.
4, the preparation method of novel high water vapor proposed by the invention barrier biodegradable composite is that melting is total Mixed method avoids the use to human body and the harmful solvent of environment in preparation process, and simple process is easy to operate, can continuously give birth to It produces, is conducive to the raising of production efficiency；Simple process, the product quality indicator between different batches are stablized, can large-scale industry Metaplasia produces, and has a wide range of application, and has wide industrialization and market prospects；Realize polymeric articles high performance and functionalization It is same, the surcharge of polymeric articles is improved, the application range of polymeric articles has been widened, is studied in composite theory It is of great significance with application and development etc..
Specific implementation method:
The present invention is further described specifically by the following examples.In following embodiment, each component Dosage is quality dosage.It is necessary to it is pointed out here that, following example only to further explanation of the invention, should not be understood as Limiting the scope of the invention, person skilled in art can carry out the present invention according to aforementioned present invention content Nonessential modifications and adaptations.
Embodiment 1
A kind of polycaprolactone (matrix)/biodegradable composite wood of glyceryl tristearate (dispersed phase) high water vapor barrier The raw material of material includes following components and parts by weight content:
Composition weight number
Polycaprolactone (for Biodegradable high molecular matrix) 80
Glyceryl tristearate (for hydrophobic biological degradation ester type compound dispersed phase) 20
The first step is stocked up by said components first；
It is 6 hours dry to be placed in 40 DEG C of vacuum drying ovens by second step for above-mentioned material；
Drying polycaprolactone that second step obtains, glyceryl tristearate are placed in high mixer premix together by third step It closes 5 minutes, revolving speed is 100 revs/min, the pre-composition of polycaprolactone and glyceryl tristearate is obtained, by pre-composition true 40 DEG C drying 3 hours in empty baking oven.
4th step, the polycaprolactone that third step is obtained and glyceryl tristearate pre-composition put into single screw extrusion machine In, pre-composition carries out melting mixing by the feed opening of extruder, conveying section, melt zone, homogenizing zone, and by width be 8mm, With a thickness of the extrusion neck ring mold of 1mm, obtains width and is 8mm, obstructs biodegradable composite with a thickness of the high water vapor of 1mm, Wherein the feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 80 DEG C, 110 DEG C, 120℃、120℃、100℃。
40 DEG C of vacuum drying ovens dryings 6 hours are first placed according to above-mentioned steps using pure polycaprolactone, then are placed in high mixer Premixing 5 minutes, wherein revolving speed is 100 revs/min, puts into single screw extrusion machine after drying 3 hours for 40 DEG C in vacuum drying oven Middle melting extrusion, and be 8mm, the extrusion neck ring mold with a thickness of 1mm by width, obtaining width is 8mm, the comparison with a thickness of 1mm Sample 1, wherein the feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 80 DEG C, 110℃、120℃、120℃、100℃。
In the above preparation method, if glyceryl tristearate is not added, pure polycaprolactone (comparative sample 1) is relatively wet Vapor permeability when degree is 50%RH is 1.7 E-13 gcmcm-2·s-1·Pa-1, when relative humidity increases to 90% After RH, vapor permeability rises to 2.7 E-13 gcmcm-2·s-1·Pa-1, barrier property reduce by 37%, illustrate pure The water vapor barrier property of polycaprolactone is unstable to the variation of ambient humidity.
The present embodiment uses hydrophobicity glyceryl tristearate as dispersed phase, scanning electron microscope test (SEM) Glyceryl tristearate is evenly dispersed in island structure in polycaprolactone as the result is shown, and obtained polycaprolactone/tri- are stearic The hydrophilic contact angle of acid glyceride composite material surface rises to 125 ° by 79 ° of pure polycaprolactone, and surface hydrophobic significantly mentions Height, when relative humidity is 50%RH, its vapor permeability is 4.6 E-14 gcmcm-2·s-1·Pa-1, with comparative sample 1 73% is improved compared to barrier property, illustrates that the vapor increased can be formed in composite inner by adding glyceryl tristearate Diffusion path, thus the vapor water barriers performance of composite material can be effectively improved；And when envionmental humidity is increased to by 50%RH When 90%RH, since polycaprolactone/glyceryl tristearate composite material hydrophobicity is largely increased, (polarity significantly drops It is low), the stronger vapor of polarity is difficult to penetrate into composite inner, can significantly reduce vapor and makees to the swelling of composite material With, so composite material vapor permeability under the conditions of 90%RH is 4.5 E-14 gcmcm-2·s-1·Pa-1, with 50% Reducing amplitude compared to barrier property under the conditions of RH is only 2%, i.e., addition glyceryl tristearate can effectively improve composite wood simultaneously Expect barrier property to the stability of humidity.
Meanwhile the tension fracture elongation rate at room temperature of comparative sample 1 and stretch modulus are respectively 840% and 193(MPa).It is poly- Caprolactone/glyceryl tristearate composite material tension fracture elongation rate at room temperature and stretch modulus be respectively 720 % and 180(MPa), mechanical property decreases compared with comparative sample 1, this is because in the dispersed phase in the composite material of island structure There are stress concentration points between glyceryl tristearate and polycaprolactone matrix, and composite material is concentrated in stress during stretching Molecule chain break and mechanical property failure first occur for point, and then are diffused into entire material, and the stretching for resulting in composite material is disconnected It splits elongation and stretch modulus decreases, but be still able to satisfy the requirement of general packaging material, this is because polycaprolactone-based Body is continuous phase, can provide good mechanical property to composite material.Therefore it is sweet to prepare polycaprolactone/tri- stearic acid for the present embodiment Grease composite material has excellent vapor water barriers performance and its barrier property has good stability to humidity, while having both good Good mechanical property, high performance and functionalization obtain unification.
As needed, the single screw extrusion machine in the present embodiment is also to use double screw extruder.
Embodiment 2
A kind of polycaprolactone (matrix)/biodegradable composite wood of glyceryl tristearate (dispersed phase) high water vapor barrier The raw material of material includes following components and parts by weight content:
Composition weight number
Polycaprolactone (for Biodegradable high molecular matrix) 70
Glyceryl tristearate (for hydrophobic biological degradation ester type compound dispersed phase) 30
The first step is stocked up by said components first；
It is 6 hours dry to be placed in 40 DEG C of vacuum drying ovens by second step for above-mentioned material；
Drying polycaprolactone that second step obtains, glyceryl tristearate are placed in high mixer premix together by third step It closes 5 minutes, revolving speed is 100 revs/min, the pre-composition of polycaprolactone and glyceryl tristearate is obtained, by pre-composition true 40 DEG C drying 3 hours in empty baking oven.
4th step, the polycaprolactone that third step is obtained and glyceryl tristearate pre-composition put into single screw extrusion machine In, pre-composition carries out melting mixing by the feed opening of extruder, conveying section, melt zone, homogenizing zone, and by width be 8mm, With a thickness of the extrusion neck ring mold of 1mm, obtains width and is 8mm, obstructs biodegradable composite with a thickness of the high water vapor of 1mm, Wherein the feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 80 DEG C, 110 DEG C, 120℃、120℃、100℃。
40 DEG C of vacuum drying ovens dryings 6 hours are first placed according to above-mentioned steps using pure polycaprolactone, then are placed in high mixer Premixing 5 minutes, wherein revolving speed is 100 revs/min, puts into single screw extrusion machine after drying 3 hours for 40 DEG C in vacuum drying oven Middle melting extrusion, and by width be 8mm, the mouth mold with a thickness of 1mm, obtain width be 8mm, the comparative sample 2 with a thickness of 1mm, Wherein the feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 80 DEG C, 110 DEG C, 120℃、120℃、100℃。
In the above preparation method, as glyceryl tristearate is not added, pure polycaprolactone (comparative sample 2) is in relative humidity Vapor permeability when for 50%RH is 1.7 E-13 gcmcm-2·s-1·Pa-1, when relative humidity increases to 90%RH When, vapor permeability rises to 2.7 E-13 gcmcm-2·s-1·Pa-1, barrier property reduces 37%, illustrates pure The vapor water barriers performance of polycaprolactone is unstable to the variation of ambient humidity.
The present embodiment uses hydrophobicity glyceryl tristearate as dispersed phase, scanning electron microscope test (SEM) Glyceryl tristearate is evenly dispersed in island structure in polycaprolactone as the result is shown, and obtained polycaprolactone/tri- are stearic The hydrophilic contact angle of acid glyceride composite material surface rises to 132 ° by 79 ° of pure polycaprolactone, illustrates that surface hydrophobic is aobvious It writes and improves, its vapor permeability is 3.1 E-14 gcmcm when relative humidity is 50%RH-2·s-1·Pa-1, with Comparative sample 2 improves 82% compared to barrier property, illustrates to add glyceryl tristearate and can be formed in composite inner to increase Water vapor diffusion path, thus the vapor water barriers performance of composite material can be effectively improved；And when envionmental humidity is by 50% When RH increases to 90%RH, since polycaprolactone/glyceryl tristearate composite material hydrophobicity is largely increased (polarity Significantly reduce), the stronger vapor of polarity is difficult to penetrate into composite inner, can significantly reduce vapor to composite material Swelling action, so composite material vapor permeability under the conditions of 90%RH is 3.15E-14 gcmcm-2·s-1·Pa-1, it is only 1.6% that vapor water barriers performance, which reduces amplitude, i.e., addition glyceryl tristearate can effectively improve composite material simultaneously Stability of the barrier property to humidity.
Meanwhile the tension fracture elongation rate at room temperature of comparative sample 2 and stretch modulus are respectively 840% and 193(MPa), gather Caprolactone/glyceryl tristearate composite material tension fracture elongation rate at room temperature and stretch modulus are respectively 680% He 172(MPa), mechanical property decreases compared with comparative sample 2, this is because in the dispersed phase in the composite material of island structure There are stress concentration points between glyceryl tristearate and polycaprolactone matrix, and composite material is concentrated in stress during stretching Molecule chain break and mechanical property failure first occur for point, and then are diffused into entire material, and the stretching for resulting in composite material is disconnected It splits elongation and stretch modulus decreases, but be still able to satisfy the requirement of general packaging material, this is because polycaprolactone-based Body is continuous phase, can provide good mechanical property to composite material.Therefore polycaprolactone manufactured in the present embodiment/tri- stearic acid Glyceride composite material has excellent vapor water barriers performance and its barrier property has good stability to humidity, has both simultaneously Good mechanical property, high performance and functionalization obtain unification.
As needed, the single screw extrusion machine in the present embodiment is also to use double screw extruder.
Embodiment 3
A kind of polylactic acid (matrix)/glyceryl tristearate (dispersed phase) high water vapor barrier biodegradable composite Raw material include following components and parts by weight content:
Composition weight number
Polylactic acid (for Biodegradable high molecular matrix) 92
Glyceryl tristearate (for hydrophobic biological degradation ester type compound dispersed phase) 8
The first step is stocked up by said components first；
Polylactic acid is placed in 80 DEG C of vacuum drying ovens dryings 6 hours by second step, and glyceryl tristearate is placed in 40 DEG C of vacuum Oven drying 6 hours；
Drying polylactic acid that second step obtains, glyceryl tristearate are placed in high mixer are pre-mixed 5 together by third step Minute, revolving speed is 100 revs/min, the pre-composition of polylactic acid and glyceryl tristearate is obtained, by pre-composition in vacuum drying oven In 40 DEG C drying 3 hours.
4th step, the polylactic acid that third step is obtained and glyceryl tristearate pre-composition are put into single screw extrusion machine, Pre-composition carries out melting mixing by the feed opening of extruder, conveying section, melt zone, homogenizing zone and is 8mm, thickness by width For the extrusion neck ring mold of 1mm, obtains width and be 8mm, obstruct biodegradable composite with a thickness of the high water vapor of 1mm, wherein The feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 150 DEG C, 160 DEG C, 170 ℃、170℃、150℃。
40 DEG C of vacuum drying ovens dryings 6 hours are first placed according to above-mentioned steps using pure polylactic acid, then are placed in high mixer pre- Mixing 5 minutes, wherein revolving speed is 100 revs/min, in vacuum drying oven in 40 DEG C of single screw extrusion machines of investment after drying 3 hours Melting extrusion, and be 8mm, the extrusion neck ring mold with a thickness of 1mm by width, obtaining width is 8mm, the comparative sample with a thickness of 1mm 3, wherein the feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 150 DEG C, 160 ℃、170℃、170℃、150℃。
In the above preparation method, if glyceryl tristearate is not added, pure polylactic acid (comparative sample 3) relatively wet Vapor permeability when degree is 50%RH is 9 E-14 gcmcm-2·s-1·Pa-1, when relative humidity increases to 90%RH, Its vapor permeability rises to 1.3 E-13 gcmcm-2·s-1·Pa-1, barrier property reduce by 31%, illustrate pure poly- cream The vapor water barriers performance of acid is unstable to the variation of ambient humidity.
The present embodiment uses hydrophobicity glyceryl tristearate as dispersed phase, scanning electron microscope test (SEM) Glyceryl tristearate is evenly dispersed in island structure in polylactic acid as the result is shown, and obtained polylactic acid/tri- stearic acid are sweet The hydrophilic contact angle of grease composite material surface rises to 85 ° by 60 ° of pure polylactic acid, and surface hydrophobic significantly improves, and works as phase Its vapor permeability is 5.8 E-14 gcmcm when being 50%RH to humidity-2·s-1·Pa-1, compared with comparative sample 3 Barrier property improves 35%, illustrates that the water vapor diffusion increased can be formed in composite inner by adding glyceryl tristearate Path, thus the vapor water barriers performance of composite material can be effectively improved；And when envionmental humidity increases to 90% by 50%RH When RH, since polylactic acid/glyceryl tristearate composite material hydrophobicity is largely increased (polarity significant decrease), polarity compared with Strong vapor is difficult to penetrate into composite inner, can significantly reduce vapor to the swelling action of composite material, so it is multiple Condensation material vapor permeability under the conditions of 90%RH is 6.2 E-14 gcmcm-2·s-1·Pa-1, under the conditions of 50%RH Reducing amplitude compared to barrier property is only 7%, i.e., addition glyceryl tristearate can effectively improve composite material barrier property simultaneously It can be to the stability of humidity.
Meanwhile the tension fracture elongation rate at room temperature of comparative sample 3 and tensile strength are respectively 25% and 65(MPa), gather cream Acid/glyceryl tristearate composite material tension fracture elongation rate at room temperature and tensile strength are respectively 23% and 59 (MPa), mechanical property decreases compared with comparative sample 3, this is because in the dispersed phase three in the composite material of island structure There are stress concentration points between tristerin and polylactic acid matrix, and composite material is in stress concentration point elder generation during stretching Molecule chain break and mechanical property failure occurs, and then is diffused into entire material, the tension failure for resulting in composite material is stretched Long rate and tensile strength decrease, but are still able to satisfy the requirement of general packaging material, this is because being in polylactic acid matrix Continuous phase can provide good mechanical property to composite material.Therefore polylactic acid manufactured in the present embodiment/tri- glycerol stearates Ester composite material has excellent vapor water barriers performance and its barrier property has good stability to humidity, while having both good Mechanical property, high performance and functionalization obtain unification.
As needed, the single screw extrusion machine in the present embodiment is also to use double screw extruder.
Embodiment 4
A kind of polylactic acid (matrix)/biodegradable composite wood of myristin (dispersed phase) high water vapor barrier The raw material of material includes following components and parts by weight content:
Composition weight number
Polylactic acid (for Biodegradable high molecular matrix) 60
Myristin (for hydrophobic biological degradation ester type compound dispersed phase) 40
The first step is stocked up by said components first；
Polylactic acid is placed in 80 DEG C of vacuum drying ovens dryings 6 hours by second step, and myristin is placed in 40 DEG C very Empty oven drying 6 hours；
Drying polylactic acid that second step obtains, myristin are placed in high mixer premix together by third step It closes 5 minutes, revolving speed is 100 revs/min, the pre-composition of polylactic acid and myristin is obtained, by pre-composition true 40 DEG C drying 3 hours in empty baking oven.
4th step, the polylactic acid that third step is obtained and myristin pre-composition put into single screw extrusion machine In, pre-composition by the feed opening of extruder, conveying section, melt zone, homogenizing zone carry out melting mixing and by width be 8mm, With a thickness of the extrusion neck ring mold of 1mm, obtains width and is 8mm, obstructs biodegradable composite with a thickness of the high water vapor of 1mm, Wherein the feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 150 DEG C, 160 ℃、170℃、170℃、150℃。
40 DEG C of vacuum drying ovens dryings 6 hours are first placed according to above-mentioned steps using pure polylactic acid, then are placed in high mixer pre- Mixing 5 minutes, wherein revolving speed is 100 revs/min, in vacuum drying oven in 40 DEG C of single screw extrusion machines of investment after drying 3 hours Melting extrusion, and be 8mm, the extrusion neck ring mold with a thickness of 1mm by width, obtaining width is 8mm, the comparative sample with a thickness of 1mm 4, wherein the feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 150 DEG C, 160 ℃、170℃、170℃、150℃。
In the above preparation method, if myristin is not added, pure polylactic acid (comparative sample 4) is relatively wet Vapor permeability when degree is 50%RH is 9 E-14 gcmcm-2·s-1·Pa-1, when relative humidity increases to 90%RH Afterwards, vapor permeability rises to 1.3 E-13 gcmcm-2·s-1·Pa-1, barrier property reduces by 31%, illustrate poly- newborn The vapor water barriers performance of acid is unstable to the variation of ambient humidity.
The present embodiment is used to myristin as dispersed phase, scanning electron microscope test (SEM) knot Fruit shows that myristin is evenly dispersed in island structure in polylactic acid, obtained polylactic acid/tri- myristic acids The hydrophilic contact angle of glyceride composite material surface rises to 115 ° by 60 ° of pure polylactic acid, illustrates that surface hydrophobic significantly mentions Height, when relative humidity is 50%RH, its vapor permeability is 1.2 E-14 gcmcm-2·s-1·Pa-1, with comparative sample 4 Compared to barrier property improve 86%, illustrate add myristin can composite inner formed increase water Steam diffusion path, thus the vapor water barriers performance of composite material can be effectively improved；And when envionmental humidity is increased by 50%RH When being added to 90%RH, since polylactic acid/myristin composite material hydrophobicity is largely increased, (polarity is significant Reduce), the stronger vapor of polarity is difficult to penetrate into composite inner, can significantly reduce swelling of the vapor to composite material Effect, so composite material vapor permeability under the conditions of 90%RH is 1.25 E-14 gcmcm-2·s-1·Pa-1, with Reducing amplitude compared to barrier property under the conditions of 50%RH is only 4%, that is, adding hydrophobic myristin can be effective Composite material barrier property is improved to the stability of humidity simultaneously.
Meanwhile the tension fracture elongation rate at room temperature of comparative sample 4 and tensile strength are respectively 25% and 65(MPa), gather cream Acid/myristin composite material tension fracture elongation rate at room temperature and tensile strength are respectively 20% and 51 (MPa), mechanical property decreases compared with comparative sample 4, this is because in the dispersed phase three in the composite material of island structure There are stress concentration points between myristic acid glyceride and polylactic acid matrix, and composite material is in stress concentration point during stretching Molecule chain break and mechanical property failure first occurs, and then is diffused into entire material, results in the tension failure of composite material Elongation and stretch modulus decrease, but are still able to satisfy the requirement of general packaging material, this is because polylactic acid matrix is Continuous phase can provide good mechanical property to composite material.Therefore polylactic acid manufactured in the present embodiment/tri- myristic acid glycerol Ester composite material has excellent vapor water barriers performance and its barrier property has good stability to humidity, while having both good Mechanical property, high performance and functionalization obtain unification.
As needed, the single screw extrusion machine in the present embodiment is also to use double screw extruder.
Embodiment 5
A kind of cellulose acetate (matrix)/glycerin monostearate (dispersed phase) high water vapor barrier is biodegradable compound The raw material of material includes following components and parts by weight content:
Composition weight number
Cellulose acetate (for Biodegradable high molecular matrix) 75
Glycerin monostearate (for hydrophobic biological degradation ester type compound dispersed phase) 25
The first step is stocked up by said components first；
Cellulose acetate is placed in 80 DEG C of vacuum drying ovens dryings 6 hours by second step, and glycerin monostearate is placed in 40 DEG C Vacuum drying oven is 6 hours dry；
Drying cellulose acetate that second step obtains, glycerin monostearate are placed in high mixer in advance by third step together Mixing 5 minutes, revolving speed are 100 revs/min, the pre-composition of cellulose acetate and glycerin monostearate are obtained, by pre-composition 40 DEG C drying 3 hours in vacuum drying oven.
4th step, the cellulose acetate that third step is obtained and glycerin monostearate pre-composition put into single screw extrusion machine In, pre-composition carries out melting mixing by the feed opening of extruder, conveying section, melt zone, homogenizing zone, and by width be 8mm, With a thickness of the extrusion neck ring mold of 1mm, obtains width and is 8mm, obstructs biodegradable composite with a thickness of the high water vapor of 1mm, Wherein the feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 160 DEG C, 170 ℃、190℃、190℃、160℃。
80 DEG C of vacuum drying ovens dryings 6 hours are first placed according to above-mentioned steps using pure cellulose acetate, then are placed in high mixer Middle premixing 5 minutes, wherein revolving speed is 100 revs/min, 40 DEG C of single screw rod extrusions of investment after drying 3 hours in vacuum drying oven Melting extrusion in machine, and be 8mm, the extrusion neck ring mold with a thickness of 1mm by width, obtaining width is 8mm, pair with a thickness of 1mm Than sample 1, wherein the feed opening of single screw extrusion machine, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 160 ℃、170℃、190℃、190℃、160℃。
In the above preparation method, if glycerin monostearate is not added, pure cellulose acetate (comparative sample 5) is opposite Vapor permeability when humidity is 50%RH is 4.4E-13 gcmcm-2·s-1·Pa-1, when relative humidity increases to 90% When RH, vapor permeability rises to 8.1 E-13 gcmcm-2·s-1·Pa-1, barrier property reduce by 46%, illustrate pure Cellulose acetate vapor water barriers performance it is unstable to the variation of ambient humidity.
The present embodiment uses hydrophobic glycerin monostearate as dispersed phase, scanning electron microscope test (SEM) glycerin monostearate is evenly dispersed in island structure in cellulose acetate as the result is shown, obtained acetate fiber Element/glycerin monostearate composite material surface hydrophilic contact angle rises to 95 ° by 50 ° of pure cellulose acetate, illustrates table Face hydrophobicity significantly improves, and when relative humidity is 50%RH, its vapor permeability is 3.1E-13 gcmcm-2·s-1· Pa-1, barrier property improves 30% compared with comparative sample 5, illustrates that addition glycerin monostearate can be in composite inner shape At the water vapor diffusion path of growth, thus the vapor water barriers performance of composite material can be effectively improved；And when environment is relatively wet Degree is when increasing to 90%RH by 50%RH, since cellulose acetate/glycerin monostearate hydrophobicity is largely increased (polarity Significantly reduce), the stronger vapor of polarity is difficult to penetrate into composite inner, can significantly reduce vapor to composite material Swelling action, so composite material vapor permeability under the conditions of 90%RH is 3.3E-13 gcmcm-2·s-1·Pa-1, It is only 6% that barrier property, which reduces amplitude, compared under the conditions of 50%RH, i.e. addition glycerin monostearate can be improved effectively simultaneously Stability of the composite material barrier property to humidity.
Meanwhile the tension fracture elongation rate at room temperature of comparative sample 5 and tensile strength are respectively 23% and 41(MPa), acetic acid Cellulose/glycerin monostearate composite material tension fracture elongation rate at room temperature and tensile strength are respectively 20% and 38 (MPa), mechanical property decreases compared with comparative sample 5, this is because in the dispersed phase list in the composite material of island structure There are stress concentration points between tristerin and cellulose acetate matrix, and composite material is concentrated in stress during stretching Molecule chain break and mechanical property failure first occur for point, and then are diffused into entire material, and the stretching for resulting in composite material is disconnected It splits elongation and stretch modulus decreases, but be still able to satisfy the requirement of general packaging material, this is because acetate base Body is continuous phase, can provide good mechanical property to composite material.Therefore cellulose acetate manufactured in the present embodiment/mono- hard Glycerol composite material has excellent vapor water barriers performance and its barrier property has good stability to humidity, simultaneously Good mechanical property is had both, high performance and functionalization obtain unification.
As needed, the single screw extrusion machine in the present embodiment is also to use double screw extruder.

Claims (5)

1. a kind of method for preparing high water vapor barrier biodegradable composite is dredged using Biodegradable high molecular as matrix Aqueous biological ester type compound of degrading is dispersed phase, is first premixed using high mixed or melting mixing technique, remelted plasticizing at Type, it is characterised in that:
(1) the Biodegradable high molecular matrix selects melt processing temperature between 80~250 DEG C, hydrophilic contact angular region is The biodegradable polyphosphazene polymer caprolactone of water-insoluble between 50 °~90 °, polylactic acid, poly-succinic fourth diester, poly- hydroxyl One of aliphatic ester, ethyl cellulose and cellulose acetate；
(2) hydrophobic biological degradation ester type compound be melt processing temperature between 80~250 DEG C, hydrophilic contact angle exists The biodegradable glycerin monostearate of water-insoluble between 90 °~150 °, glyceryl tristearate, ethylene glycol list are stearic Acid esters, glyceryl monolaurate, laurin, single nutmeg acid glyceride, myristin, palmitic acid One of ester；
(3) the hydrophilic contact angle of the degradation of hydrophobic biological selected in system ester type compound is than Biodegradable high molecular matrix High 20 ° of hydrophilic contact angle or more；
(4) Biodegradable high molecular matrix and hydrophobic biological degradation ester type compound dispersed phase described in are by weight percentage 50~99%:50~1% carries out ingredient.
2. the method according to claim 1 for preparing high water vapor barrier biodegradable composite, it is characterised in that Described mixed hybrid technique using height and premix refers to Biodegradable high molecular matrix and hydrophobic biological degradation esters chemical combination The mixing that object dispersed phase carries out in high mixer.
3. the method according to claim 1 for preparing high water vapor barrier biodegradable composite, it is characterised in that The use melting mixing technique carries out premix and refers to Biodegradable high molecular matrix and hydrophobic biological degradation esters chemical combination The melting mixing and granulation process that object dispersed phase carries out in an extruder, wherein extruding and feeding mouth, conveying section, melt zone, homogenizing Section, the processing temperature of mouth mold are respectively 40~200 DEG C, 80~250 DEG C, 80~250 DEG C, 80~250 DEG C, 70~250 DEG C.
4. the method according to claim 1,2 or 3 for preparing high water vapor barrier biodegradable composite, feature It is that the fusion plastification molding refers to the esters that will degrade by Biodegradable high molecular matrix, the hydrophobic biological of premix It closes object dispersed phase and carries out melting mixing in an extruder, and obstructed by the high water vapor that different shape mouth mold obtains required size Biodegradable composite, wherein feed opening, conveying section, melt zone, homogenizing zone, mouth mold processing temperature be respectively 40~ 200 DEG C, 80~250 DEG C, 80~250 DEG C, 80~250 DEG C, 70~250 DEG C.
5. the method according to claim 1,2 or 3 for preparing high water vapor barrier biodegradable composite, feature It is that the fusion plastification molding refers to the esters that will degrade by Biodegradable high molecular matrix, the hydrophobic biological of premix It closes object dispersed phase and carries out fusion plastification in mixer, processing temperature is 80~250 DEG C, and rotor speed is 15~60rpm, modeling The change time is 3~12min；And the material after fusion plastification is placed in corresponding mould, through vulcanizing press temperature 80~ 250 DEG C, it is hot-forming under conditions of 6~15MPa of pressure, it is cooling, high water vapor can be obtained and obstruct biodegradable composite wood Material.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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