CN103897244B - The preparation method of graphene oxide with high barrier-polyethylene nano compound film - Google Patents
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- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
Abstract
The preparation method of graphene oxide with high barrier-polyethylene nano compound film, heats the graphene oxide ultrasonic disperse of modification in dimethylbenzene, then adds high density polyethylene(HDPE) and stirs and obtain ODA-GO/HDPE mixing solutions; Ultrahigh molecular weight polyethylene(UHMWPE) film dimethylbenzene is cleaned, after dimethylbenzene evaporation, by the mode of dipping in film, UHMWPE film is immersed in the ODA-GO/HDPE mixing solutions of heat, then dry, repeat this step, until reach the required number of plies, to obtain final product.The graphene oxide with high barrier that the present invention prepares-polyethylene nano compound film security is high, the feature of environmental protection is good, saturating Oxygen Coefficients have dropped about 49%, there is superelevation oxygen-barrier property, numerous food, the requirement of drug packaging and the purposes of other products can be met, and technique is simple, with low cost, there is practicality and promotional value widely.
Description
Technical field
The invention belongs to high molecule nano composite material preparing technical field, be specifically related to the preparation method of a kind of graphene oxide with high barrier-polyethylene nano compound film.
Background technology
In recent years, olefin polymer is because of the mechanical property of its excellence, outstanding moulding processability, good chemical stability and cheap etc., obtain in food, pharmaceuticals packaging and apply more and more widely, but not good the becoming of barrier properties for gases restricts its key issue applied in packaging, for meeting the need of market, improves the important directions that its gas barrier property has become research.At present, the method improving polymer barrier property mainly contains vacuum evaporation, multi-layer co-extruded compound and laminar nano filler compound.Wherein, laminar nano filler compound is the focus of people's concern in recent years, this system is " multipath effect " or " nanometer barrier wall effect " that utilize polymkeric substance and the good interface interaction of filler and nanoscale twins filler in polymeric matrix, cause gas-permeable, effectively improve the barrier property of polymeric matrix, though the method has the plurality of advantages such as easy to process, product cost is high, but also there is the problem that Nano filling and polymer-based carbon body interface are not easily combined, its film forming thickness is also uncontrollable, limits the range of application of this technology.
Layer-by-layer is the method preparing order thin film that development in recent years is got up.It utilizes the electrostatic adhesion characteristic of organic or inorganic zwitterion, forms film by the alternately molecule deposition of gegenion system.This technology has film forming not by restrictions such as substrate kind, shape, sizes, chemical constitution and the thickness of film are controlled, preparation process is simple, facilitates scale operation, and these advantages make LBL self-assembly film become the study hotspot of scientific circles' raising polymer barrier performance.
Patent CN101474897A discloses a kind of grapheme-organic material layered assembling film and preparation method thereof.It is for raw material with grapheme material and organic materials, utilize the interactions such as the electrostatic between Graphene and organic materials, hydrogen bond, coordinate bond or Charger transfer, to be layering film forming by method for manufacturing thin film such as spin coating, spraying, dipping-lifts, every tunic is thick can be controlled at 10nm-2mm as required.Feature utilizes the electricity of Graphene uniqueness, magnetic, mechanics and chemical property, according to the difference of selected organic materials, prepare the multilayered film material with difference in functionality, can be used as the manufacture of biomaterial, electro-conductive material, electromagnetic shielding and absorbing material, Precision Instrument and Machinery device.
The present invention, by comprehensive stratiform Nano filling compound and layer-by-layer, provides the preparation method of a kind of graphene oxide with high barrier-polyethylene nano compound film.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of graphene oxide with high barrier-polyethylene nano compound film, layer-by-layer is adopted to make the nano compound film with structure layer by layer, have superelevation oxygen-barrier property its, and security is high, and the feature of environmental protection is good.
The technical solution adopted in the present invention is, the preparation method of graphene oxide with high barrier-polyethylene nano compound film, and concrete steps are as follows:
Step 1, graphene oxide (GO) 0.1 ~ 0.3g Hummer method of modification prepared to be dispersed in 80 ~ 120ml distilled water and ultrasonic agitation 1 ~ 2h, alcohol mixeding liquid containing 1 ~ 2g octadecylamine (ODA) is joined in GO suspension and also at room temperature stir 24 ~ 30h, by the product cleaning purification then vacuum-drying under 55 ~ 65 DEG C of conditions repeatedly in water-ethanol mixed solution obtained, obtain ODA-GO;
Step 2, ODA-GO ultrasonic disperse step 1 obtained is in 150 ~ 200ml dimethylbenzene and be heated to 135 ~ 145 DEG C, then by high density polyethylene(HDPE) (HDPE) grain dissolution of 15 ~ 25mg in above-mentioned solution and continuously stirring, finally obtain the ODA-GO/HDPE mixing solutions of heat;
Step 3, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film dimethylbenzene is cleaned, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 2 obtained by the mode of dipping in film, then dry 3 ~ 5min in an oven, repeats this step, is layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
Feature of the present invention is also,
The detailed process that the Hummer method of modification in step 1 prepares graphene oxide is:
The first step, takes 3 ~ 5gK first respectively
2s
2o
8, 3 ~ 5gP
2o
5with 5 ~ 7g powdered graphite, mixing, then add 20 ~ 30ml vitriol oil and be cooled to room temperature after constant temperature stirring 4 ~ 5h at 75 ~ 85 DEG C, stir 12 ~ 14 hours after adding 1 ~ 1.5L distilled water, with the micropore filter paper filtering of 0.4 ~ 0.5 μm to remove residual part acid, product drying 24 ~ 30h can be obtained the graphite of preoxidation;
Second step, the graphite of the preoxidation the first step obtained is added in 240 ~ 250ml vitriol oil, constantly stirs and add 25 ~ 35gKMnO in ice bath
4, stir after 2 ~ 3h at 30 ~ 40 DEG C and add 450 ~ 550ml distilled water diluting, continue stirring 1 ~ 2h, then add 1 ~ 1.5L distilled water, continue to stir, finally add 40 ~ 50ml, 25 ~ 35% H
2o
2it is light yellow that solution continues to be stirred to solution, filters, washing, and drying obtains graphite oxide at 50 ~ 60 DEG C in a vacuum;
3rd step, the graphite oxide obtained by second step is dissolved in the distilled water of 100 ~ 200ml, and ultrasonic disperse 30 ~ 40min, obtains graphene oxide.
In step 1, in water-ethanol mixed solution, the volume ratio of water and ethanol is 1:1.
The invention has the beneficial effects as follows, the preparation method of graphene oxide with high barrier of the present invention-polyethylene nano compound film, main employing layer-by-layer, polyethylene film is immersed in (135 ~ 145 DEG C) mixing solutions of heat, repeatedly makes the nano compound film with structure layer by layer; The graphene oxide with high barrier prepared-polyethylene nano compound film security is high, the feature of environmental protection is good, saturating Oxygen Coefficients have dropped about 49%, there is superelevation oxygen-barrier property, numerous food, the requirement of drug packaging and the purposes of other products can be met, and technique is simple, with low cost, there is practicality and promotional value widely.
Accompanying drawing explanation
Fig. 1 is the permeable model figure of gas in graphene oxide with high barrier of the present invention-polyethylene nano compound film preparation method;
Fig. 2 is the SEM figure of graphene oxide with high barrier-polyethylene nano compound film prepared by embodiment 1;
Fig. 3 is the FTIR curve of graphene oxide and amino modified graphene oxide in embodiment 1;
Fig. 4 is the XRD curve of graphene oxide and amino modified graphene oxide in embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The preparation method of graphene oxide with high barrier of the present invention-polyethylene nano compound film, concrete steps are as follows:
Step 1, the Hummer method of modification prepares graphene oxide
First respectively 3 ~ 5gK is taken
2s
2o
8, 3 ~ 5gP
2o
5with 5 ~ 7g powdered graphite, mixing, then add 20 ~ 30ml vitriol oil and be cooled to room temperature after constant temperature stirring 4 ~ 5h at 75 ~ 85 DEG C, stir 12 ~ 14 hours after adding 1 ~ 1.5L distilled water, with the micropore filter paper filtering of 0.4 ~ 0.5 μm to remove residual part acid, product drying 24 ~ 30h can be obtained the graphite of preoxidation;
The graphite of preoxidation is added in 240 ~ 250ml vitriol oil, constantly stirs and add 25 ~ 35gKMnO in ice bath
4, stir after 2 ~ 3h at 30 ~ 40 DEG C and add 450 ~ 550ml distilled water diluting, continue stirring 1 ~ 2h, then add 1 ~ 1.5L distilled water, continue to stir, finally add 40 ~ 50ml, 25 ~ 35% H
2o
2it is light yellow that solution continues to be stirred to solution, filters, washing, and drying obtains graphite oxide at 50 ~ 60 DEG C in a vacuum;
Be dissolved in by graphite oxide in the distilled water of 100 ~ 200ml, ultrasonic disperse 30 ~ 40min, obtains graphene oxide;
Step 2, graphene oxide (GO) 0.1 ~ 0.3g step 1 prepared to be dispersed in 80 ~ 120ml distilled water and ultrasonic agitation 1 ~ 2h, alcohol mixeding liquid containing 1 ~ 2g octadecylamine (ODA) is joined in GO suspension and also at room temperature stir 24 ~ 30h, the product obtained repeatedly is cleaned then vacuum-drying under 55 ~ 65 DEG C of conditions of purifying in water-ethanol mixed solution (volume ratio of water and ethanol is 1:1), obtains ODA-GO;
Step 3, ODA-GO ultrasonic disperse step 2 obtained is in 150 ~ 200ml dimethylbenzene and be heated to 135 ~ 145 DEG C, then by high density polyethylene(HDPE) (HDPE) grain dissolution of 15 ~ 25mg in above-mentioned solution and continuously stirring, finally obtain the ODA-GO/HDPE mixing solutions of heat;
Step 4, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film dimethylbenzene is cleaned, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 2 obtained by the mode of dipping in film, then dry 3 ~ 5min in an oven, repeats this step, is layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
The mechanism of action of the present invention is: gas molecule infiltration be in the film an absorption, dissolving, diffusion and separate out microprocess.First gas molecule contacts with film, dissolves subsequently at film surface enrichment, thus both sides, film surface produce concentration ladder.Under the effect of concentration difference, " moment hole " that gas molecule occurs using macromolecular chain segment strenuous exercise progressively at film internal diffusion as passage, finally arrives the opposite side of film and separates out, the general mechanism of Here it is film breathable.
Amino modified graphene oxide, under Ultrasonic Heating effect, can be dispersed in xylene solution, and forms mixed uniformly suspension with high-density polyethylene powder, and hot submersion process makes to form good interface effect between mixing solutions and film.
As shown in Figure 1, because modified graphene oxide skeleton is combined closely by carbon atom to form, when gas molecule runs into graphene oxide lamella, directly can not penetrate, can only walk around along modified graphene oxide lamella direction, this makes the permeable area of gas reduce; And spacing between modified graphene oxide lamella is very little, the modified graphene oxide lamella added makes gas diffusion path become from the direction of vertical film the direction being parallel to film, and the permeation pathway of gas is increased.The effect of modified graphene oxide nanometer barrier wall significantly improves the barrier property of ultrahigh molecular weight polyethylene(UHMWPE) film, makes the saturating Oxygen Coefficients of the nano compound film containing modified graphene oxide have dropped 48.7 times.
The preparation method of graphene oxide with high barrier of the present invention-polyethylene nano compound film, main employing layer-by-layer, polyethylene film is immersed in (135 ~ 145 DEG C) mixing solutions of heat, repeatedly makes the nano compound film with structure layer by layer; The graphene oxide with high barrier prepared-polyethylene nano compound film security is high, the feature of environmental protection is good, saturating Oxygen Coefficients have dropped about 49%, there is superelevation oxygen-barrier property, numerous food, the requirement of drug packaging and the purposes of other products can be met, and technique is simple, with low cost, there is practicality and promotional value widely.
Embodiment 1
Step 1, the preparation of graphene oxide
First respectively 5gK is taken
2s
2o
8, 5gP
2o
5with 6g powdered graphite, mixing, then adds the 25ml vitriol oil and constant temperature is cooled to room temperature after stirring 5 hours at 80 DEG C, stirs 12 hours after adding 1L distilled water, with the micropore filter paper filtering of 0.45 μm to remove residual part acid, namely product drying is obtained the graphite of preoxidation for 24 hours;
The graphite of preoxidation is added in the 250ml vitriol oil, constantly stirs and add 30gKMnO in ice bath
4, stir after 2 hours at 40 DEG C and add 500ml distilled water diluting, continue stirring 2 hours, then add 1.5L distilled water, continue to stir, finally add 40ml, 30% H
2o
2it is light yellow that solution continues to be stirred to solution, filters, washing, and drying obtains graphite oxide at 60 DEG C in a vacuum;
Be dissolved in by graphite oxide in the distilled water of 150ml, ultrasonic disperse 30min, obtains graphene oxide;
Step 2, the modification of graphene oxide
Graphene oxide (GO) 0.2g step 1 prepared to be dispersed in 100ml distilled water and ultrasonic agitation 1.5h, alcohol mixeding liquid containing 1.5g octadecylamine (ODA) is joined in GO suspension and also at room temperature stir 24 hours, the product obtained repeatedly is cleaned then vacuum-drying at 60 DEG C of purifying in water-ethanol mixed solution (volume ratio of water and ethanol is 1:1), obtains ODA-GO;
Step 3, ODA-GO ultrasonic disperse step 2 obtained is in 200ml dimethylbenzene and be heated to 140 DEG C, then by high density polyethylene(HDPE) (HDPE) grain dissolution of 20mg in above-mentioned solution and continuously stirring, finally obtain the ODA-GO/HDPE mixing solutions of heat;
Step 4, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film dimethylbenzene is cleaned, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 3 obtained by the mode of dipping in film, then in an oven dry 3 minutes, repeat this step, be layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
Fig. 2 is the SEM figure of graphene oxide with high barrier-polyethylene nano compound film prepared by embodiment 1, and can find out, modified graphene oxide (ODA-GO) to be evenly distributed on ultrahigh molecular weight polyethylene(UHMWPE) film and to have structure layer by layer.
Fig. 3 is the FTIR curve of graphene oxide and amino modified graphene oxide in embodiment 1; As can be seen from Figure 3, containing a large amount of oxygen-containing functional groups in graphene oxide, wherein 3421 ~ 3438cm
-1, 1720cm
-1, 1624 ~ 1650cm
-1with 1030 ~ 1160cm
-1place is respectively the stretching vibration peak of carboxyl (-O-C=O), carbonyl (C=O) and epoxy group(ing) (C-O-C), 2920cm
-1and 2851cm
-1for CH
2with the C-H stretching vibration peak of CH group.Compared with the infrared spectrogram of graphene oxide, modified graphene oxide is at 2920/2851cm
-1the peak intensity at place significantly raises, and show the carbonyl condensation reaction of amino by octadecylamine and surface of graphene oxide, a large amount of alkyl chain is grafted to surface of graphene oxide.In addition, modified graphene oxide is at 1560cm
-1(the bending acid amides of N-H), 1460/1472cm
-1(C-N stretches acid amides) and 721cm
-1the vibration peak at (C-H flexural vibration) place shows to there is amido linkage between graphene oxide lamella and octadecyl amine molecule, and graphene oxide is by successful modification.
Fig. 4 is the XRD curve of graphene oxide and amino modified graphene oxide in embodiment 1.As can be seen from Figure 4, graphene oxide shows typical diffracted absorption peak in 2 θ=10.1 °.According to Bragg equation formula: 2dsin θ=n λ can obtain the interlamellar spacing d=0.88nm of graphene oxide, compares original graphite interlamellar spacing d=0.34nm, illustrate that oxidising process makes graphite surface and edge introduce a large amount of oxy radical.Octadecyl modified graphene oxide shows typical diffracted absorption peak in 2 θ=3.78 °, d=2.33nm, and diffraction peak diminishes, sheet interlayer spacing becomes large, i.e. successful grafting ODA molecular chain.
The saturating Oxygen Coefficients of pure ultra-high molecular mass polyethylene film is 7.50 × 10
-14cm
3cm/ (cm
2and the saturating Oxygen Coefficients of graphene oxide with high barrier-polyethylene nano compound film prepared by embodiment 1 is 1.54 × 10 sPa),
-15cm
3cm/ (cm
2sPa), have dropped about 48.7 times.
Embodiment 2
Step 1, the preparation of graphene oxide
First respectively 4gK is taken
2s
2o
8, 3gP
2o
5with 5g powdered graphite, mixing, then adds the 20ml vitriol oil and constant temperature is cooled to room temperature after stirring 4 hours at 85 DEG C, stirs 14 hours after adding 1.2L distilled water, with the micropore filter paper filtering of 0.40 μm to remove residual part acid, namely product drying is obtained the graphite of preoxidation for 28 hours;
The graphite of preoxidation is added in the 240ml vitriol oil, constantly stirs and add 35gKMnO in ice bath
4, stir after 3 hours at 35 DEG C and add 450ml distilled water diluting, continue stirring 1.5 hours, then add 1.0L distilled water, continue to stir, finally add 50ml, 25% H
2o
2it is light yellow that solution continues to be stirred to solution, filters, washing, and drying obtains graphite oxide at 50 DEG C in a vacuum;
Be dissolved in by graphite oxide in the distilled water of 100ml, ultrasonic disperse 40min, obtains graphene oxide;
Step 2, the modification of graphene oxide
Graphene oxide (GO) 0.3g step 1 prepared to be dispersed in 120ml distilled water and ultrasonic agitation 2h, alcohol mixeding liquid containing 1.0g octadecylamine (ODA) is joined in GO suspension and also at room temperature stir 28 hours, the product obtained repeatedly is cleaned then vacuum-drying at 55 DEG C of purifying in water-ethanol mixed solution (volume ratio of water and ethanol is 1:1), obtains ODA-GO;
Step 3, ODA-GO ultrasonic disperse step 2 obtained is in 150ml dimethylbenzene and be heated to 135 DEG C, then by high density polyethylene(HDPE) (HDPE) grain dissolution of 15mg in above-mentioned solution and continuously stirring, finally obtain the ODA-GO/HDPE mixing solutions of heat;
Step 4, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film dimethylbenzene is cleaned, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 3 obtained by the mode of dipping in film, then in an oven dry 4 minutes, repeat this step, be layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
Embodiment 3
Step 1, the preparation of graphene oxide
First respectively 3gK is taken
2s
2o
8, 4gP
2o
5with 7g powdered graphite, mixing, then adds the 30ml vitriol oil and constant temperature is cooled to room temperature after stirring 4.5 hours at 75 DEG C, stirs 13 hours after adding 1.5L distilled water, with the micropore filter paper filtering of 0.5 μm to remove residual part acid, namely product drying is obtained the graphite of preoxidation for 30 hours;
The graphite of preoxidation is added in the 245ml vitriol oil, constantly stirs and add 25gKMnO in ice bath
4, stir after 2.5 hours at 30 DEG C and add 550ml distilled water diluting, continue stirring 1 hour, then add 1.2L distilled water, continue to stir, finally add 45ml, 35% H
2o
2it is light yellow that solution continues to be stirred to solution, filters, washing, and drying obtains graphite oxide at 55 DEG C in a vacuum;
Be dissolved in by graphite oxide in the distilled water of 200ml, ultrasonic disperse 35min, obtains graphene oxide;
Step 2, the modification of graphene oxide
Graphene oxide (GO) 0.1g step 1 prepared to be dispersed in 80ml distilled water and ultrasonic agitation 1h, alcohol mixeding liquid containing 2g octadecylamine (ODA) is joined in GO suspension and also at room temperature stir 30 hours, the product obtained repeatedly is cleaned then vacuum-drying at 65 DEG C of purifying in water-ethanol mixed solution (volume ratio of water and ethanol is 1:1), obtains ODA-GO;
Step 3, ODA-GO ultrasonic disperse step 2 obtained is in 180ml dimethylbenzene and be heated to 145 DEG C, then by high density polyethylene(HDPE) (HDPE) grain dissolution of 25mg in above-mentioned solution and continuously stirring, finally obtain the ODA-GO/HDPE mixing solutions of heat;
Step 4, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) film dimethylbenzene is cleaned, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 3 obtained by the mode of dipping in film, then in an oven dry 5 minutes, repeat this step, be layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film.
Claims (2)
1. the preparation method of graphene oxide with high barrier-polyethylene nano compound film, it is characterized in that, concrete steps are as follows:
Step 1, graphene oxide 0.1 ~ 0.3g prepared by the Hummer method of modification to be dispersed in 80 ~ 120ml distilled water and ultrasonic agitation 1 ~ 2h, alcohol mixeding liquid containing 1 ~ 2g octadecylamine is joined in GO suspension and also at room temperature stirs 24 ~ 30h, by the product cleaning purification then vacuum-drying under 55 ~ 65 DEG C of conditions repeatedly in water-ethanol mixed solution obtained, obtain ODA-GO;
Step 2, ODA-GO ultrasonic disperse step 1 obtained is in 150 ~ 200ml dimethylbenzene and be heated to 135 ~ 145 DEG C, then by the high density polyethylene(HDPE) grain dissolution of 15 ~ 25mg in above-mentioned mixing solutions and continuously stirring, finally obtain the ODA-GO/HDPE mixing solutions of heat;
Step 3, ultrahigh molecular weight polyethylene(UHMWPE) film dimethylbenzene is cleaned, after dimethylbenzene evaporation, in ODA-GO/HDPE mixing solutions UHMWPE film immersion step 2 obtained by the mode of dipping in film, then dry 3 ~ 5min in an oven, repeats this step, is layering, until reach the required number of plies, finally obtain graphene oxide with high barrier-polyethylene nano compound film;
The detailed process that the Hummer method of modification in step 1 prepares graphene oxide is:
The first step, takes 3 ~ 5gK first respectively
2s
2o
8, 3 ~ 5gP
2o
5with 5 ~ 7g powdered graphite, mixing, then add 20 ~ 30ml vitriol oil and be cooled to room temperature after constant temperature stirring 4 ~ 5h at 75 ~ 85 DEG C, stir 12 ~ 14 hours after adding 1 ~ 1.5L distilled water, with the micropore filter paper filtering of 0.4 ~ 0.5 μm to remove residual part acid, product drying 24 ~ 30h can be obtained the graphite of preoxidation;
Second step, the graphite of the preoxidation the first step obtained is added in 240 ~ 250ml vitriol oil, constantly stirs and add 25 ~ 35gKMnO in ice bath
4, stir after 2 ~ 3h at 30 ~ 40 DEG C and add 450 ~ 550ml distilled water diluting, continue stirring 1 ~ 2h, then add 1 ~ 1.5L distilled water, continue to stir, finally add 40 ~ 50ml, 25 ~ 35% H
2o
2it is light yellow that solution continues to be stirred to solution, filters, washing, and drying obtains graphite oxide at 50 ~ 60 DEG C in a vacuum;
3rd step, the graphite oxide obtained by second step is dissolved in the distilled water of 100 ~ 200ml, and ultrasonic disperse 30 ~ 40min, obtains graphene oxide.
2. the preparation method of graphene oxide with high barrier according to claim 1-polyethylene nano compound film, is characterized in that, in step 1, in water-ethanol mixed solution, the volume ratio of water and ethanol is 1:1.
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| CN109401018A (en) * | 2018-11-05 | 2019-03-01 | 上海赢知信息科技有限公司 | A kind of high density polyethylene bellows and preparation method thereof |
| CN110240763B (en) * | 2019-05-23 | 2022-03-15 | 大连工业大学 | Method for preparing bromobutyl rubber/polyethylene barrier function composite membrane by wet method |
| CN110563989B (en) * | 2019-09-06 | 2021-07-16 | 江南大学 | Preparation method of ultrahigh molecular weight polyethylene composite material |
| CN113813796B (en) * | 2021-08-27 | 2022-11-29 | 浙江大学 | Nano composite dispersion liquid, high-gas-barrier nano composite film and preparation method thereof |
| CN114456470A (en) * | 2022-03-09 | 2022-05-10 | 中海石油(中国)有限公司 | Polymer composite material with gas high-barrier property |
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| CN101474897A (en) * | 2009-01-16 | 2009-07-08 | 南开大学 | Grapheme-organic material layered assembling film and preparation method thereof |
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