CN109401153A - A kind of polyvinyl alcohol/graphene composition microcellular foam material - Google Patents
A kind of polyvinyl alcohol/graphene composition microcellular foam material Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C08J9/0023—Use of organic additives containing oxygen
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
A kind of the present invention relates to cell stabilities good, not givey polyvinyl alcohol/graphene composition microcellular foam material.The foamed material is made by polyvinyl alcohol/graphene composition by supercritical fluid foaming technique, the composition includes polyvinyl alcohol, isocyanate group graphene and plasticiser, when polyvinyl alcohol in composition is 100 mass parts, isocyanate group graphene is 0.1~5.0 mass parts, and plasticiser is 5~30 mass parts.Polyvinyl alcohol of the invention/graphene composition microcellular foam material, compared with simple polyvinyl alcohol foam material, have the advantages that isocyanate group graphene can reduce the free energy barrier of cell nucleation, heterogeneous nucleation site is provided for polyvinyl alcohol foam, improve cell nucleation rate, abscess is not easy to collapse in foaming process, has more superior mechanical performance than pure polyvinyl alcohol foam.
Description
Technical field
The present invention relates to a kind of polymer micro foamed material, it is more particularly to that a kind of cell stability is good, is not easy to collapse
Polyvinyl alcohol/graphene composition microcellular foam material.
Background technique
Polymer micro foamed material is a kind of material of superior performance, has light, heat-insulated, sound insulation, buffering, specific strength
The advantages that high, cheap, therefore obtained in fields such as packing business, industry, agricultural, transportation, war industry, aerospace industries
To being widely applied.Usually used foam of polymers is made of petroleum base resin mostly, such as polypropylene, polyethylene, polyphenyl
Ethylene, polyurethane and polyvinyl chloride etc..With the raising of environmental consciousness, biodegradable polymers foam is increasingly by people
Concern.Polyvinyl alcohol is a kind of environmentally friendly material, and great amount of hydroxy group is contained on strand, and combustion product is water and titanium dioxide
Carbon, environmental pollution are small.As a kind of typical biodegradable and water-soluble polymer, polyvinyl alcohol has superior synthesis
Performance, such as chemical stability, mechanical performance, hot property and barrier property, application field is extensive, with other degradable polymer phases
It is more lower than price, it is more cost effective.
As for polyvinyl alcohol foam technique, conventional chemical foaming agent such as fluorochlorohydrocarbon and hydrogen are replaced using the foaming agent of environmental protection
Fluorochlorohydrocarbon etc. is an essential job.Supercritical carbon dioxide due to its non-toxic inexpensive, non-combustible, chemical inertness and easily
In being obtained from air, gradually become by green foaming agent concerned by people.Currently, supercritical carbon dioxide foaming technology is wide
In the general production for microporous polymer.
But during supercritical carbon dioxide foaming, polyvinyl alcohol by intrinsic viscoplasticity, weak melt strength,
The influence of the factors such as the low solubility of carbon dioxide and low nucleation efficiencies, it is difficult to obtain high cell density and not givey bubble
Foam.The polyvinyl alcohol foam prepared under relatively high pressure and temperature simultaneously tends to collapse within a few hours, comprehensive
Desired value can be still below such as the mechanical performance of cell density.
Summary of the invention
The object of the present invention is to provide a kind of inexpensive, not givey polyvinyl alcohol/graphene composition foamed materials.
The inventors of the present invention pass through in-depth study, as a result, it has been found that: it is added by the way that the graphene containing isocyanate group will be had
In polyvinyl alcohol/graphene composition, while regulating and controlling supercritical fluid foaming parameters, not givey polyethylene can be made
Alcohol/graphene composition microcellular foam material.
That is, the present invention relates to a kind of polyvinyl alcohol/graphene composition microcellular foam material, the polyvinyl alcohol/graphite
Ene compositions include polyvinyl alcohol, isocyanate group graphene and plasticiser, the polyethylene in polyvinyl alcohol/graphene composition
When alcohol is 100 mass parts, isocyanate group graphene is 0.1~5.0 mass parts, and plasticiser is 5~30 mass parts.
Polyvinyl alcohol of the invention/graphene composition microcellular foam material, with simple polyvinyl alcohol foam material phase
Than having the advantages that isocyanate group graphene can reduce the free energy barrier of cell nucleation, being provided for polyvinyl alcohol foam
Cell nucleation rate is improved in heterogeneous nucleation site, and abscess is not easy to collapse in foaming process, has more than pure polyvinyl alcohol foam
Superior mechanical performance.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the foamed sample inner cell form of embodiment 1.
Fig. 2 is after the foamed sample of comparative example 1 places 12h, the photo obviously collapsed occur.
Specific embodiment
In the following, the present invention is described in detail.
The present invention relates to a kind of polyvinyl alcohol/graphene composition microcellular foam material, the polyvinyl alcohol/graphene composition
Comprising polyvinyl alcohol, isocyanate group graphene and plasticiser, the polyvinyl alcohol in polyvinyl alcohol/graphene composition is 100
When mass parts, isocyanate group graphene is 0.1~5.0 mass parts, and plasticiser is 5~30 mass parts.
As the polyvinyl alcohol for constituting composition, the degree of polymerization can be 500~2500, preferably 1700~2000.This hair
The alcoholysis degree of polyvinyl alcohol in bright can be 74~99%, and specific alcoholysis degree can according to need end properties and determine:
For the sample for needing low temperature water-soluble, preferably alcoholysis degree is 74~88%, not water-soluble for low temperature, needs high temperature water-soluble and obstructs
Property good sample, preferably alcoholysis degree is 89~99%, further preferred 95~99%.Furthermore it is possible to which it is poly- to adulterate two or more
Vinyl alcohol, to obtain appropriate performance.The viscosity of the higher melt of molecular weight is bigger, and when high temperature easier degradation, melt-processed is got over
It is difficult.Therefore the present invention is according to different polyvinyl alcohol molecule amounts and alcoholysis degree, can be using not same amount and different types of
Processing aid.
Graphene used in the present invention is the graphene of hydroxyl, and hydroxyl graphene can directly be bought by commercial channel,
Hydroxy radical content is not particularly limited, and when usual hydroxyl graphene is 100 mass parts, hydroxyl is 0.1~3.0 mass parts.Can be
Graphene with single or multi-layer structure, area are 4~50 μm2, with a thickness of 0.5~10nm, specific surface area 20m2/ g~
800m2/ g, preferred single layer graphene, single-layer graphene specific surface area is bigger, therefore preferably.The preparation of isocyanate group graphene
Method is not particularly limited, and can be prepared by chemic modified method, that is, is utilized containing the silane coupler modified of isocyanate group
Conventional hydroxy graphene.
The selection of the silane coupling agent is not particularly limited, usually optional 3- isocyanatopropyl triethoxysilane and
It is one or two kinds of in 3- isocyanate group trimethoxy silane.
The preparation method of isocyanate group graphene, can be as follows, using 500mL ethyl alcohol and 500mL distilled water as mixing
2g graphene is added to above-mentioned in the mixed solvent and ultrasound keeps its evenly dispersed, adds 1~10mL silane coupling agent by solvent
And 5~30mL ammonium hydroxide, at room temperature 6~12h of mechanical stirring, then mixed solution is centrifuged, obtained precipitating distilled water and nothing
Water-ethanol washs 3~5 times, is finally dried in vacuo product at 60~80 DEG C, obtains isocyanate group graphene.
When polyvinyl alcohol in polyvinyl alcohol/graphene composition is 100 mass parts, isocyanate group graphene is 0.1
~5.0 mass parts.With the increase of isocyanate group graphene content, the free energy barrier of cell nucleation is reduced, and increases out-phase
Nucleation site increases cell nucleation rate, to increase cell density and reduce abscess-size, therefore lower limit is more preferably
0.5 mass parts, more preferable 1.0 mass parts, when isocyanate group graphene too high levels, due to the Van der Waals force of nanoparticle,
It is also easy to produce reunion, therefore the upper limit is more preferably 2.0 mass parts.
When polyvinyl alcohol in polyvinyl alcohol/graphene composition is 100 mass parts, plasticiser is 5~30 mass parts.Make
For the plasticiser for constituting composition, be not particularly limited, optional spent glycol, polyethylene glycol, glycerine, pentaerythrite, in oneself
Amide, propylene glycol, trimethylolpropane, pentanediol, sorbierite, water, ethanol amine, diethanol amine, acetamide, dimethylformamide
With one of ethylenediamine or a variety of, it is contemplated that the viscosity and higher of plasticiser are convenient for thermoplastic processing, plasticiser preferably third
One or both of three pure and mild pentanediols.If selecting glycerine and pentanediol, the mass mixing ratio of glycerine and pentanediol
It can be 1: 2~2: 1, consider from thermoplasticity processing effect and operation ease angle, preferably 1: 1.With the increasing of content of plasticizing agent
Add, melting temperature and crystallinity are substantially reduced, however easily occur mutually to separate when plasticiser dosage is excessive, therefore plasticiser is into one
Step is preferably 10~25 mass parts.
In the polyvinyl alcohol/graphene composition can also contain one or both of cerium salt and ruthenium salt, due to cerium,
Ruthenium metal ion can play coordination in the composition, facilitate the formation that polyvinyl alcohol consolidates network, after facilitating foaming
The promotion of cell stability, common cerium salt have cerous nitrate, cerous acetate and cerium oxalate, and common ruthenium salt has nitric acid ruthenium and acetic acid ruthenium,
From the point of view of the validity of stable bubble hole, further preferred ruthenium salt.The additive amount of cerium salt and/or ruthenium salt, is not particularly limited, and leads to
When polyvinyl alcohol in normal polyvinyl alcohol/graphene composition is 100 mass parts, additive amount is 0.1~1 mass parts.
Other processing aids can be also added in polyvinyl alcohol/graphene composition, including one in nucleating agent, heat stabilizer
Kind is a variety of.The additive amount of processing aid, is not particularly limited, and is with the polyvinyl alcohol in polyvinyl alcohol/graphene composition
When 100 mass parts, the additive amount of auxiliary agent can be 1~20 mass parts, preferably 5~10 mass parts.Additive amount within this range, can
To take into account processing type and polyvinyl alcohol/graphene composition microcellular foam material cell density.
The nucleating agent can be inorganic nucleator such as talcum powder, calcium carbonate, montmorillonite, clay, mica, it is preferable that institute
The partial size for stating inorganic nucleator can be 200~3000 mesh, preferably 1000~3000 mesh, moisture content≤0.5%, or have
Machine nucleating agent, such as carboxylic acid and its metallic salt, glucitols, aryl phosphoric acids salt, rosin acid soaps or high molecular nucleating agent
As one or more in the polyethylene glycol of molecular weight 400~1000, HEC (PVA0588).It can also be according to different abscess needs
Determine the partial size and dosage of nucleating agent.
Polyvinyl alcohol/graphene composition preparation method, is not particularly limited, and usually first prepares plasticiser, then will
Graphene, processing aid etc. are added in plasticiser and are stirred by ultrasonic, and obtain filler plasticizing solution, then by polyvinyl alcohol powder
Material or pellet are added in above-mentioned filler plasticizing solution, are sufficiently stirred, are obtained polyvinyl alcohol/graphene composition pellet.
In addition, can also squeeze out polyvinyl alcohol/graphene composition pellet by screw extruder, required composition shape is obtained
Shape.
Polyvinyl alcohol/graphene composition microporous foam process, is not particularly limited, can be such that by polyvinyl alcohol/
Graphene composition is placed in Belt-type tools, is warming up to saturation temperature, and saturation temperature is 130 DEG C~165 DEG C, is filled with overcritical
For fluid to saturation pressure, saturation pressure is 10~18MPa, then heat-insulation pressure keeping, and the heat-insulation pressure keeping time is 30~120min, is then unloaded
Pressure, is prepared polyvinyl alcohol/graphene composition microcellular foam material, and decompression rate is 50~500MPa/s.
The Belt-type tools are the high pressure resistant mold of stainless steel, including cope plate and lower template.
The supercritical fluid can be the mixing of supercritical carbon dioxide, supercritical nitrogen or their arbitrary proportion
Gas considers, preferably supercritical carbon dioxide from the convenience of industry.
The saturation temperature can be 130~165 DEG C.With the raising of saturation temperature, cell wall thins down and easy
In rupture, when temperature is too high, due to lower melt strength, it may occur that abscess merges.Meanwhile average cell size with
The raising of temperature and increase, cell density accordingly reduces, therefore preferably 130~150 DEG C of saturation temperature.
The saturation pressure is 10~18MPa.For given temperature, the solubility of carbon dioxide in the polymer matrix
Increase with the increase of saturation pressure, in addition, higher saturation pressure helps to reduce nucleation energy barrier, and then generates more
Abscess.With the increase of saturation pressure, average cell size is reduced, and cell density increases, and saturation pressure further preferred 14~
18MPa。
The heat-insulation pressure keeping time can be more preferably 50~80min.
The decompression rate, can be more preferably 200~500MPa/s, and higher decompression rate can trigger quickly
Nucleation, foaming, are conducive to the control to smaller aperture due and the raising of hole density.
Analysis test method used in the present invention is as follows:
Apparent density and expansion ratio test
The density of foaming product and foaming raw material is measured by densimeter, and this method utilizes Archimedes buoyancy method principle.First
Measure the actual mass m of testgas, then measure quality m when sample is completely immersed in waterwater, sample is calculated using formula 1
Apparent density ρf:
ρ in formulawaterFor the density of sample in water, unit g/cm3。
Expansion ratio refers to the ratio of volume and the front volume that foams after foaming, according to the density of foaming sample and foaming raw material, by formula 2
The expansion ratio of foamed material can be found out
ρ in formulagasDensity before indicating polymer foaming, unit: g/cm3, ρfDensity after indicating polymer foaming, unit: g/
cm3。
Foamed sample microstructure observing
After foamed sample is impregnated 2min in liquid nitrogen, then quick brittle failure carries out metal spraying to brittle failure face, then scanning electron microscope again
Lower observation fracture morphology and foam structure choose the SEM picture that can represent the different multiples of the sample foam structure.
Cell density, bubble aperture diameter and distribution calculate
Stereoscan photograph is handled using PaintShop Image-pro, counts abscess-size, abscess-size is hair
The average diameter for steeping sample abscess, is directly calculated by software；Cell density is abscess on area per cubic centimeter in foamed sample
Number, be calculated by formula 3:
The abscess number counted in n electromicroscopic photograph in formula, unit: a；
A indicates statistics area selected in electromicroscopic photograph, unit: cm3；
Indicate the expansion ratio of foamed material.
Sample collapses rate calculating
The initial volume V of sample is measured by drainage0, after sample is placed 12h, drainage is recycled to measure volume at this time
V1, rate W is collapsed using the calculating sample of formula 4.
W is smaller it can be seen from formula 4, and sample is more not easy to collapse.
Embodiment 1
Using 500mL ethyl alcohol and 500mL distilled water as mixed solvent, 2g hydroxyl graphene is added to above-mentioned in the mixed solvent simultaneously
Ultrasound keeps its evenly dispersed, adds 2.5mL3- isocyanatopropyl triethoxysilane and 10mL ammonium hydroxide, machinery stirs at room temperature
12h is mixed, then mixed solution is centrifuged, obtained precipitating distilled water and dehydrated alcohol wash 5 times, finally that product is true at 60 DEG C
Sky is dry, obtains isocyanate group graphene.
By mixing glycerol and pentanediol acquisition plasticiser with 1: 1 ratio, by 1.0g isocyanate group graphene dispersion in 14g
In plasticiser, then ultrasonic agitation 85g polyvinyl alcohol powder (PVA1799, alcoholysis degree 99%, permanent auspicious chemical industry) is added again
Wherein, it is vigorously stirred 1h at 60 DEG C, obtains polyvinyl alcohol/graphene composition.By screw machine extruder obtain with a thickness of
0.5 centimetre of sheet polyethylene alcohol/graphene composition.
Sheet polyethylene alcohol/graphene composition (4cm × 4cm × 0.5cm) is placed in Belt-type tools, saturation temperature is warming up to
Degree, saturation temperature are 145 DEG C, are filled with supercritical carbon dioxide to saturation pressure, saturation pressure 14MPa, then heat-insulation pressure keeping, protect
Polyvinyl alcohol/graphene composition microcellular foam material is prepared in warm pressure maintaining 60min, then release, and decompression rate is
500MPa/s。
The foamed material being prepared, by its inner cell pattern of scanning electron microscope analysis, measuring average pore size is 34.7 μm, meter
It is 8.1 × 10 that calculation, which obtains cell density,7cells/cm3。
What is calculated collapses rate to sample are as follows: 8.3%.
Embodiment 2
By mixing glycerol and pentanediol acquisition plasticiser with 1: 1 ratio, by isocyanates foundation stone made from 1.0g embodiment 1
Black alkene and 0.5g nitric acid ruthenium are dispersed in 14g plasticiser, ultrasonic agitation, then again by 85g polyvinyl alcohol powder (PVA1799, alcohol
Xie Du is 99%, permanent auspicious chemical industry) it is added thereto, it is vigorously stirred 1h at 60 DEG C, obtains polyvinyl alcohol/graphene composition.It is logical
It crosses screw machine extruder and obtains sheet polyethylene alcohol/graphene composition with a thickness of 0.5 centimetre.
Sheet polyethylene alcohol/graphene composition (4cm × 4cm × 0.5cm) is placed in Belt-type tools, saturation temperature is warming up to
Degree, saturation temperature are 145 DEG C, are filled with supercritical carbon dioxide to saturation pressure, saturation pressure 14MPa, then heat-insulation pressure keeping, protect
Polyvinyl alcohol/graphene composition microcellular foam material is prepared in warm pressure maintaining 60min, then release, and decompression rate is
500MPa/s。
The foamed material being prepared measures 32.8 μm of average pore size by its inner cell pattern of scanning electron microscope analysis, calculates
Obtaining cell density is 8.7 × 107cells/cm3。
What is calculated collapses rate to sample are as follows: 6.4%.
Comparative example 1
By mixing glycerol and pentanediol acquisition plasticiser with 1: 1 ratio, 85g polyvinyl alcohol powder lot dispersing is plasticized in 14g
In agent, it is vigorously stirred 1h at 60 DEG C, obtains polyvinyl alcohol compositions.It is obtained by screw machine extruder with a thickness of 0.5 centimetre
Sheet polyethylene alcohol composition.
Sheet polyethylene alcohol composition (4cm × 4cm × 0.5cm) is placed in Belt-type tools, saturation temperature is warming up to, is saturated
Temperature is 145 DEG C, is filled with supercritical carbon dioxide to saturation pressure, saturation pressure 14MPa, then heat-insulation pressure keeping, heat-insulation pressure keeping
Polyvinyl alcohol micropore foamed material, decompression rate 500MPa/s is prepared in 60min, then release.
The foamed material being prepared, measuring average pore size is 48.1 μm, and it is 3.8 × 10 that cell density, which is calculated,7cells/
cm3。
What is calculated collapses rate to sample are as follows: 42.1%.Sample after collapsing, as shown in Fig. 2, there is fold very serious on surface,
Thickness of sample is thinned serious.
Claims (5)
1. a kind of polyvinyl alcohol/graphene composition microcellular foam material, the polyvinyl alcohol/graphene composition includes poly- second
Enol, isocyanate group graphene and plasticiser, when the polyvinyl alcohol in polyvinyl alcohol/graphene composition is 100 mass parts,
Isocyanate group graphene is 0.1~5.0 mass parts, and plasticiser is 5~30 mass parts.
2. polyvinyl alcohol described in claim 1/graphene composition microcellular foam material, the alcoholysis degree of polyvinyl alcohol is 95%
~99%.
3. polyvinyl alcohol described in claim 1/graphene composition microcellular foam material, wherein plasticiser be glycerine and
One or both of pentanediol.
4. polyvinyl alcohol described in claim 1/graphene composition microcellular foam material, wherein plasticiser be glycerine and
The mass mixing ratio of pentanediol, glycerine and pentanediol is 1: 2~2: 1.
5. polyvinyl alcohol described in claim 1/graphene composition microcellular foam material, wherein polyvinyl alcohol/graphene group
Closing also includes one or both of cerium salt and ruthenium salt in object, and the polyvinyl alcohol in polyvinyl alcohol/graphene composition is 100 matter
When measuring part, the additive amount of cerium salt and/or ruthenium salt is 0.1~1 mass parts.
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| CN110423331A (en) * | 2019-08-05 | 2019-11-08 | 中电保力（北京）科技有限公司 | A kind of water-swellable flexible flame retardant foamed plastics and preparation method thereof |
| CN110883068A (en) * | 2019-12-16 | 2020-03-17 | 湖州合达图宏新材料技术有限公司 | Plasticizing method of solid waste |
| CN114736476A (en) * | 2022-03-27 | 2022-07-12 | 宁波大学 | Polyvinyl alcohol conductive microporous foam material |
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