CN116120685A - Polyvinyl alcohol composite material and preparation method thereof - Google Patents
Polyvinyl alcohol composite material and preparation method thereof Download PDFInfo
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- CN116120685A CN116120685A CN202211666966.XA CN202211666966A CN116120685A CN 116120685 A CN116120685 A CN 116120685A CN 202211666966 A CN202211666966 A CN 202211666966A CN 116120685 A CN116120685 A CN 116120685A
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 75
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- -1 quaternary ammonium salt modified montmorillonite Chemical class 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims description 75
- 238000003756 stirring Methods 0.000 claims description 48
- 239000006185 dispersion Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 30
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 24
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 206010013642 Drooling Diseases 0.000 claims description 7
- 208000008630 Sialorrhea Diseases 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
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- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 230000020477 pH reduction Effects 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- QQGISFDJEJMKIL-JAIQZWGSSA-N (5z)-5-[[3-(hydroxymethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical compound C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1CO QQGISFDJEJMKIL-JAIQZWGSSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention provides a polyvinyl alcohol composite material and a preparation method thereof, wherein the polyvinyl alcohol composite material comprises the following components in percentage by mass: 90% -95% of polyvinyl alcohol; 1% -10% of acidulated modified carbon nano tube; 1 to 5 percent of quaternary ammonium salt modified montmorillonite. The polyvinyl alcohol composite material has excellent electromagnetic shielding performance and flame retardance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyvinyl alcohol composite material and a preparation method thereof.
Background
Sensitive components in electronic equipment can be damaged due to instantaneous overvoltage generated by radiation, and non-metal components of a power system can also fail due to radiation, so that electromagnetic protection work of the electronic components is particularly important. Polyvinyl alcohol (PVA) has good biocompatibility, can be decomposed into carbon dioxide, water and some other low-molecular compounds by microorganisms in the nature after being used, has no pollution to the environment, and is an ideal green high polymer. But has poor heat resistance, inflammability and poor electromagnetic shielding performance, and limits the application of the material in certain fields.
At present, most researches mainly aim at improving the thermal performance, the mechanical performance and the water resistance of the polyvinyl alcohol composite material, but few researches report how to improve the electromagnetic shielding performance and the flame retardant performance of the polyvinyl alcohol, and the polyvinyl alcohol composite material is applied to the field of electronic equipment.
Therefore, how to improve the electromagnetic shielding performance and the flame retardant performance of the polyvinyl alcohol so as to be suitable for the electronic equipment is a technical problem which needs to be solved by the technicians in the field.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a polyvinyl alcohol composite material, the components of which include, in mass fraction: 90% -95% of polyvinyl alcohol; 1% -10% of acidulated modified carbon nano tube; 1 to 5 percent of quaternary ammonium salt modified montmorillonite.
In a first aspect, the acidified modified carbon nanotubes are obtained by: adding carbon nano tubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, magnetically stirring to obtain a dispersion liquid with the concentration of 2-5g/100mL, heating the dispersion liquid to 100 ℃ and then reacting for 2 hours; cooling after the reaction is finished, soaking and washing the mixture to the pH value of 7-8 by distilled water, and carrying out suction filtration, drying and grinding to obtain the acidified modified carbon nano tube.
In the first aspect, in the mixed solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.
in a first aspect, the quaternary ammonium salt modified montmorillonite is obtained by: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an ester group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, condensing and refluxing for 2-4 hours to obtain a uniform suspension liquid; and carrying out ultrasonic treatment on the suspension liquid to uniformly disperse the suspension liquid, then carrying out centrifugal separation to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified montmorillonite.
In a second aspect, the present application provides a method for preparing a polyvinyl alcohol composite material, the method comprising the steps of: preparing a modified carbon nano tube; preparing modified montmorillonite; according to the material formula, the material comprises the following components in percentage by mass: 90-95% of polyvinyl alcohol, 1-10% of modified carbon nano tube and 1-5% of modified montmorillonite, and weighing the components; mixing the modified carbon nano tube and the modified montmorillonite, adding deionized water, and carrying out ultrasonic oscillation for 30min at 50-55 ℃ to obtain a modified carbon nano tube/modified montmorillonite dispersion liquid; placing polyvinyl alcohol into a three-neck flask, adding deionized water, placing into a water bath kettle, stirring and heating to 90-100 ℃, and magnetically stirring for 1h until polyvinyl alcohol particles are completely dissolved; adding a modified carbon nano tube/modified montmorillonite dispersion liquid into the three-neck flask, and continuously heating and stirring for 2-3h to form uniform and transparent viscous liquid; and (3) drooling the viscous liquid on a glass dish to form a film, naturally air-drying at room temperature, solidifying a coating film on a glass slide, transferring the glass dish into a vacuum drying oven, and drying at 80 ℃ for 4 hours to obtain the polyvinyl alcohol composite material.
In a second aspect, the modified carbon nanotubes are acidified modified carbon nanotubes.
In a second aspect, preparing the acidified modified carbon nanotubes comprises: adding carbon nano tubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, magnetically stirring to obtain a dispersion liquid with the concentration of 2-5g/100mL, heating the dispersion liquid to 100 ℃ and then reacting for 2 hours; cooling after the reaction is finished, soaking and washing the mixture to the pH value of 7-8 by distilled water, and carrying out suction filtration, drying and grinding to obtain the acidified modified carbon nano tube.
In the second aspect, in the mixed solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.
in a second aspect, the modified montmorillonite is a quaternary ammonium salt modified montmorillonite.
In a second aspect, preparing the quaternary ammonium salt modified montmorillonite comprises: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an ester group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, condensing and refluxing for 2-4 hours to obtain a uniform suspension liquid; and carrying out ultrasonic treatment on the suspension liquid to uniformly disperse the suspension liquid, then carrying out centrifugal separation to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified montmorillonite.
The beneficial effects are that: the invention provides a polyvinyl alcohol composite material which consists of 90-95% of polyvinyl alcohol, 1-10% of acidification modified carbon nano tubes and 1-5% of quaternary ammonium salt modified montmorillonite by mass fraction. The invention selects the modified carbon nano tube and montmorillonite as modifier, which has good compatibility with the base material. The acidized and modified carbon nano tube can effectively improve the interface acting force between the carbon nano tube and the resin matrix, the hollow structure of the carbon nano tube can increase the dissipation path of electromagnetic waves, enhance the interface polarization effect and improve the electromagnetic shielding performance of the polyvinyl alcohol material; the quaternary ammonium salt modified montmorillonite is a silicate material with a multilayer structure, has good barrier effect, plays a certain role in heat insulation, and greatly improves the flame retardance of the polyvinyl alcohol material.
Drawings
In order to more clearly illustrate the embodiments of the present description or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing a polyvinyl alcohol composite material according to an embodiment of the invention;
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
Meanwhile, throughout the specification, unless otherwise specifically indicated, the terms used herein should be construed as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
It should be noted that the symbol "/" between two materials referred to in the present invention means "and", for example, "modified carbon nanotubes/modified montmorillonite" means "modified carbon nanotubes and modified montmorillonite".
Example 1
The polyvinyl alcohol composite material is obtained according to the following method:
(1) According to the material formula, the material comprises the following components in percentage by mass: 90% of polyvinyl alcohol, 8% of acidified modified carbon nano tube and 2% of quaternary ammonium salt modified montmorillonite; accurately weighing the components;
wherein, the acidification modified carbon nano tube is obtained by the following steps: adding carbon nano tubes into the mixed solution of concentrated sulfuric acid and concentrated nitric acid, and magnetically stirring to obtain a dispersion liquid with the concentration of 2-5g/100 mL; in the mixed solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1, a step of; heating the dispersion liquid to 100 ℃ and then reacting for 2 hours; cooling after the reaction is finished, soaking and washing the mixture to the pH value of 7-8 by distilled water, and carrying out suction filtration, drying and grinding to obtain the acidified modified carbon nano tube; the quaternary ammonium salt modified montmorillonite is obtained by the following steps: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an ester group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, condensing and refluxing for 2-4 hours to obtain a uniform suspension liquid; carrying out ultrasonic treatment on the suspension to uniformly disperse the suspension, then centrifugally separating to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain quaternary ammonium salt modified montmorillonite;
(2) Mixing the acidified modified carbon nano tube and the quaternary ammonium salt modified montmorillonite, adding 50mL of deionized water, and carrying out ultrasonic vibration for 30min at 50-55 ℃ to obtain a modified carbon nano tube/modified montmorillonite dispersion liquid;
(3) Placing polyvinyl alcohol into a 250mL three-neck flask, adding 100mL deionized water, placing into a water bath kettle, stirring and heating to 90-100 ℃, and magnetically stirring for 1h until polyvinyl alcohol particles are completely dissolved;
(4) Adding a modified carbon nano tube/modified montmorillonite dispersion liquid into the three-neck flask, and continuously heating and stirring for 2-3h to form uniform and transparent viscous liquid;
(5) And (3) drooling the viscous liquid on a glass dish to form a film, naturally air-drying at room temperature, solidifying the film on a glass slide to a certain extent, transferring the glass dish into a vacuum drying oven, and drying at 80 ℃ for 4 hours to obtain the polyvinyl alcohol composite material.
Example 2
The polyvinyl alcohol composite material is obtained according to the following method:
(1) According to the material formula, the material comprises the following components in percentage by mass: 90% of polyvinyl alcohol, 7.5% of acidified modified carbon nano tube and 2.5% of quaternary ammonium salt modified montmorillonite; accurately weighing the components;
wherein, the acidification modified carbon nano tube is obtained by the following steps: adding carbon nano tubes into the mixed solution of concentrated sulfuric acid and concentrated nitric acid, and magnetically stirring to obtain a dispersion liquid with the concentration of 2-5g/100 mL; in the mixed solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1, a step of; heating the dispersion liquid to 100 ℃ and then reacting for 2 hours; cooling after the reaction is finished, soaking and washing the mixture to the pH value of 7-8 by distilled water, and carrying out suction filtration, drying and grinding to obtain the acidified modified carbon nano tube; the quaternary ammonium salt modified montmorillonite is obtained by the following steps: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an ester group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, condensing and refluxing for 2-4 hours to obtain a uniform suspension liquid; carrying out ultrasonic treatment on the suspension to uniformly disperse the suspension, then centrifugally separating to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain quaternary ammonium salt modified montmorillonite;
(2) Mixing the acidified modified carbon nano tube and the quaternary ammonium salt modified montmorillonite, adding 50mL of deionized water, and carrying out ultrasonic vibration for 30min at 50-55 ℃ to obtain a modified carbon nano tube/modified montmorillonite dispersion liquid;
(3) Placing polyvinyl alcohol into a 250mL three-neck flask, adding 100mL deionized water, placing into a water bath kettle, stirring and heating to 90-100 ℃, and magnetically stirring for 1h until polyvinyl alcohol particles are completely dissolved;
(4) Adding a modified carbon nano tube/modified montmorillonite dispersion liquid into the three-neck flask, and continuously heating and stirring for 2-3h to form uniform and transparent viscous liquid;
(5) And (3) drooling the viscous liquid on a glass dish to form a film, naturally air-drying at room temperature, solidifying the film on a glass slide to a certain extent, transferring the glass dish into a vacuum drying oven, and drying at 80 ℃ for 4 hours to obtain the polyvinyl alcohol composite material.
Example 3
The polyvinyl alcohol composite material is obtained according to the following method:
(1) According to the material formula, the material comprises the following components in percentage by mass: 90% of polyvinyl alcohol, 5% of acidified modified carbon nano tube and 5% of quaternary ammonium salt modified montmorillonite; accurately weighing the components;
wherein, the acidification modified carbon nano tube is obtained by the following steps: adding carbon nano tubes into the mixed solution of concentrated sulfuric acid and concentrated nitric acid, and magnetically stirring to obtain a dispersion liquid with the concentration of 2-5g/100 mL; in the mixed solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1, a step of; heating the dispersion liquid to 100 ℃ and then reacting for 2 hours; cooling after the reaction is finished, soaking and washing the mixture to the pH value of 7-8 by distilled water, and carrying out suction filtration, drying and grinding to obtain the acidified modified carbon nano tube; the quaternary ammonium salt modified montmorillonite is obtained by the following steps: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an ester group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, condensing and refluxing for 2-4 hours to obtain a uniform suspension liquid; carrying out ultrasonic treatment on the suspension to uniformly disperse the suspension, then centrifugally separating to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain quaternary ammonium salt modified montmorillonite;
(2) Mixing the acidified modified carbon nano tube and the quaternary ammonium salt modified montmorillonite, adding 50mL of deionized water, and carrying out ultrasonic vibration for 30min at 50-55 ℃ to obtain a modified carbon nano tube/modified montmorillonite dispersion liquid;
(3) Placing polyvinyl alcohol into a 250mL three-neck flask, adding 100mL deionized water, placing into a water bath kettle, stirring and heating to 90-100 ℃, and magnetically stirring for 1h until polyvinyl alcohol particles are completely dissolved;
(4) Adding a modified carbon nano tube/modified montmorillonite dispersion liquid into the three-neck flask, and continuously heating and stirring for 2-3h to form uniform and transparent viscous liquid;
(5) And (3) drooling the viscous liquid on a glass dish to form a film, naturally air-drying at room temperature, solidifying the film on a glass slide to a certain extent, transferring the glass dish into a vacuum drying oven, and drying at 80 ℃ for 4 hours to obtain the polyvinyl alcohol composite material.
In order to further demonstrate the inventive aspects of the present invention, polyvinyl alcohol composites can be prepared as described in examples 1-3 above, the present invention uses comparative examples 1-3 as follows in comparison with examples 1-3.
Comparative example 1
The polyvinyl alcohol material is obtained according to the following method:
(1) Precisely weighing 100% of polyvinyl alcohol with the mass percentage of 100% according to a material formula;
(2) Placing polyvinyl alcohol into a 250mL three-neck flask, adding 100mL deionized water, placing into a water bath kettle, stirring and heating to 90-100 ℃, and magnetically stirring for 1h until polyvinyl alcohol particles are completely dissolved;
(3) Heating and stirring for 2-3h;
(4) And casting saliva on a glass dish to form a film, naturally air-drying at room temperature, curing the film on a glass slide to a certain extent, transferring the glass dish into a vacuum drying oven, and drying for 4 hours at the temperature of 80 ℃ to obtain the polyvinyl alcohol material.
Comparative example 2
The polyvinyl alcohol material is obtained according to the following method:
(1) According to the material formula, the material comprises the following components in percentage by mass: 90% of polyvinyl alcohol and 10% of acidified modified carbon nano tubes; accurately weighing the components;
wherein, the acidification modified carbon nano tube is obtained by the following steps: adding carbon nano tubes into the mixed solution of concentrated sulfuric acid and concentrated nitric acid, and magnetically stirring to obtain a dispersion liquid with the concentration of 2-5g/100 mL; in the mixed solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1, a step of; heating the dispersion liquid to 100 ℃ and then reacting for 2 hours; cooling after the reaction is finished, soaking and washing the mixture to the pH value of 7-8 by distilled water, and carrying out suction filtration, drying and grinding to obtain the acidified modified carbon nano tube;
(2) Adding 50mL of deionized water into the acidified modified carbon nano tube, and performing ultrasonic vibration for 30min at 50-55 ℃ to obtain a dispersion liquid of the modified carbon nano tube;
(3) Placing polyvinyl alcohol into a 250mL three-neck flask, adding 100mL deionized water, placing into a water bath kettle, stirring and heating to 90-100 ℃, and magnetically stirring for 1h until polyvinyl alcohol particles are completely dissolved;
(4) Adding the dispersion liquid of the modified carbon nano tube into the three-neck flask, and continuously heating and stirring for 2-3h to form uniform and transparent viscous liquid;
(5) And (3) drooling the viscous liquid on a glass dish to form a film, naturally air-drying at room temperature, solidifying the film on a glass slide to a certain extent, transferring the glass dish into a vacuum drying oven, and drying at 80 ℃ for 4 hours to obtain the polyvinyl alcohol material.
Comparative example 3
The polyvinyl alcohol material is obtained according to the following method:
(1) According to the material formula, the material comprises the following components in percentage by mass: 90% of polyvinyl alcohol and 10% of quaternary ammonium salt modified montmorillonite; accurately weighing the components;
wherein the quaternary ammonium salt modified montmorillonite is obtained by the following steps: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an ester group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, condensing and refluxing for 2-4 hours to obtain a uniform suspension liquid; carrying out ultrasonic treatment on the suspension to uniformly disperse the suspension, then centrifugally separating to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain quaternary ammonium salt modified montmorillonite;
(2) Adding 50mL of deionized water into the quaternary ammonium salt modified montmorillonite, and carrying out ultrasonic vibration for 30min at 50-55 ℃ to obtain a modified montmorillonite dispersion liquid;
(3) Placing polyvinyl alcohol into a 250mL three-neck flask, adding 100mL deionized water, placing into a water bath kettle, stirring and heating to 90-100 ℃, and magnetically stirring for 1h until polyvinyl alcohol particles are completely dissolved;
(4) Adding the dispersion liquid of the modified montmorillonite into the three-neck flask, and continuously heating and stirring for 2-3h to form uniform and transparent viscous liquid;
(5) And (3) drooling the viscous liquid on a glass dish to form a film, naturally air-drying at room temperature, solidifying the film on a glass slide to a certain extent, transferring the glass dish into a vacuum drying oven, and drying at 80 ℃ for 4 hours to obtain the polyvinyl alcohol composite material.
Effect examples
The materials prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance test, and the test results are shown in Table 1.
Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
Electromagnetic shielding effectiveness/dB | 35.6 | 36.8 | 34.7 | 19.5 | 25.8 | 24.6 |
UL94 flame retardance | V0 | V0 | V0 | HB | V1 | V1 |
TABLE 1 Material Performance test results for examples 1-3 and comparative examples 1-3
As can be obtained from table 1, the polyvinyl alcohol composite materials developed by compounding polyvinyl alcohol, acidified modified carbon nanotubes and quaternary ammonium salt modified montmorillonite in different proportions in examples 1 to 3 of the invention are excellent in flame retardant property and electromagnetic shielding property. The acidized modified carbon nanotubes are uniformly dispersed in the polyvinyl alcohol matrix, and a good space conductive network is formed by winding and interleaving, so that the dissipation path of electromagnetic waves can be increased, the interface polarization effect is enhanced, the electromagnetic wave loss capacity is effectively improved, and the polyvinyl alcohol composite material has higher electromagnetic shielding efficiency; the organic cations in the quaternary ammonium salt surfactant are exchanged by ions to replace the original hydrated cations among montmorillonite layers, so that the montmorillonite has better properties of lipophilicity, organic compatibility, thermal stability and the like, the interlayer spacing of the montmorillonite is effectively opened, and the compatibility of the montmorillonite and organic matters is improved. The interlayer spacing of silicate increases, and polymer chains in a molten state are more likely to enter between the sheets when melt extrusion is performed. The silicate sheet layer covers the surface of the material, plays a role in heat insulation, and effectively improves the flame retardant property of the polyvinyl alcohol material.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The polyvinyl alcohol composite material is characterized by comprising the following components in percentage by mass:
90% -95% of polyvinyl alcohol; 1% -10% of acidulated modified carbon nano tube; 1 to 5 percent of quaternary ammonium salt modified montmorillonite.
2. The polyvinyl alcohol composite according to claim 1, wherein the acidified modified carbon nanotubes are obtained by: adding carbon nano tubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, magnetically stirring to obtain a dispersion liquid with the concentration of 2-5g/100mL, heating the dispersion liquid to 100 ℃ and then reacting for 2 hours; cooling after the reaction is finished, soaking and washing the mixture to the pH value of 7-8 by distilled water, and carrying out suction filtration, drying and grinding to obtain the acidified modified carbon nano tube.
3. The polyvinyl alcohol composite material according to claim 2, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed solution is 3:1.
4. the polyvinyl alcohol composite according to claim 3, wherein the quaternary ammonium salt modified montmorillonite is obtained by: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an ester group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, condensing and refluxing for 2-4 hours to obtain a uniform suspension liquid; and carrying out ultrasonic treatment on the suspension liquid to uniformly disperse the suspension liquid, then carrying out centrifugal separation to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified montmorillonite.
5. The preparation method of the polyvinyl alcohol composite material is characterized by comprising the following steps of:
preparing a modified carbon nano tube;
preparing modified montmorillonite;
according to the material formula, the material comprises the following components in percentage by mass: 90-95% of polyvinyl alcohol, 1-10% of modified carbon nano tube and 1-5% of modified montmorillonite, and weighing the components;
mixing the modified carbon nano tube and the modified montmorillonite, adding deionized water, and performing ultrasonic vibration at 50-55 ℃ for 30min to obtain a modified carbon nano tube/modified montmorillonite dispersion;
placing polyvinyl alcohol into a three-neck flask, adding deionized water, placing into a water bath kettle, stirring and heating to 90-100 ℃, and magnetically stirring for 1h until polyvinyl alcohol particles are completely dissolved;
adding a modified carbon nano tube/modified montmorillonite dispersion liquid into the three-neck flask, and continuously heating and stirring for 2-3h to form uniform and transparent viscous liquid;
and (3) drooling the viscous liquid on a glass dish to form a film, naturally air-drying at room temperature, solidifying a coating film on a glass slide, transferring the glass dish into a vacuum drying oven, and drying at 80 ℃ for 4 hours to obtain the polyvinyl alcohol composite material.
6. The method of claim 5, wherein the modified carbon nanotubes are acidified modified carbon nanotubes.
7. The method of preparing a polyvinyl alcohol composite according to claim 6, wherein preparing the acidified modified carbon nanotubes comprises: adding carbon nano tubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, magnetically stirring to obtain a dispersion liquid with the concentration of 2-5g/100mL, heating the dispersion liquid to 100 ℃ and then reacting for 2 hours; cooling after the reaction is finished, soaking and washing the mixture to the pH value of 7-8 by distilled water, and carrying out suction filtration, drying and grinding to obtain the acidified modified carbon nano tube.
8. The method for preparing a polyvinyl alcohol composite material according to claim 7, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed solution is 3:1.
9. the method for preparing a polyvinyl alcohol composite material according to claim 8, wherein the modified montmorillonite is a quaternary ammonium salt modified montmorillonite.
10. The method for preparing a polyvinyl alcohol composite material according to claim 9, wherein preparing the quaternary ammonium salt modified montmorillonite comprises: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an ester group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, condensing and refluxing for 2-4 hours to obtain a uniform suspension liquid; and carrying out ultrasonic treatment on the suspension liquid to uniformly disperse the suspension liquid, then carrying out centrifugal separation to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified montmorillonite.
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CN103160049A (en) * | 2012-12-07 | 2013-06-19 | 河南城建学院 | Preparation method for nano-silver/carbon nano-tube (CNT)/polyvinyl alcohol (PVA) composite electroconductive film |
CN115490954A (en) * | 2022-08-29 | 2022-12-20 | 湖北合聚新材料有限公司 | Polypropylene composite material and preparation method and application thereof |
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