CN114805689A - Preparation method of nano-cellulose reinforced polyvinylidene fluoride composite material - Google Patents
Preparation method of nano-cellulose reinforced polyvinylidene fluoride composite material Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 140
- 239000001913 cellulose Substances 0.000 title claims abstract description 140
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 51
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 238000012545 processing Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 209
- 239000000843 powder Substances 0.000 claims description 56
- 239000004113 Sepiolite Substances 0.000 claims description 37
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 37
- 239000000835 fiber Substances 0.000 claims description 37
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 37
- 239000011707 mineral Substances 0.000 claims description 37
- 229910052624 sepiolite Inorganic materials 0.000 claims description 37
- 235000019355 sepiolite Nutrition 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000000227 grinding Methods 0.000 claims description 28
- 235000011837 pasties Nutrition 0.000 claims description 28
- 239000002159 nanocrystal Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 239000012467 final product Substances 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 18
- 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 claims description 16
- 239000006084 composite stabilizer Substances 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000003063 flame retardant Substances 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 239000002121 nanofiber Substances 0.000 claims description 16
- 239000013543 active substance Substances 0.000 claims description 14
- 239000012986 chain transfer agent Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 229920001046 Nanocellulose Polymers 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 108010059892 Cellulase Proteins 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229940106157 cellulase Drugs 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 238000006266 etherification reaction Methods 0.000 claims description 4
- 101710112457 Exoglucanase Proteins 0.000 claims description 3
- 238000007385 chemical modification Methods 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 239000002923 metal particle Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 108010047754 beta-Glucosidase Proteins 0.000 description 1
- 102000006995 beta-Glucosidase Human genes 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention discloses a preparation method of a nano-cellulose reinforced polyvinylidene fluoride composite material, and particularly relates to the technical field of a vinylidene fluoride polymer composite material, and the preparation method specifically comprises the following steps: step 10, preparing raw materials; step 20, processing the nano-cellulose; step 30, pretreating vinylidene fluoride monomers; step 40, additive pretreatment; and step 50, carrying out polymerization reaction. The composite material sequentially formed by connecting the metal particles by using the network structure of the organic group in water and stabilizing the metal particles further increases the organic characteristics on the basis of keeping the characteristics of the polyvinylidene fluoride compound, and simultaneously greatly improves the tensile strength of the material, and has the advantages of simple process, low equipment requirement and strong operability.
Description
Technical Field
The invention relates to the technical field of a vinylidene fluoride polymer composite material, in particular to a preparation method of a nano-cellulose reinforced polyvinylidene fluoride composite material.
Background
Cellulose Nanofibers (CNF) and Cellulose Nanocrystals (CNC) are collectively called as nanocelluloses, and since cellulose nanofibers can be dispersed in water into a three-dimensional network structure, particles can be dispersed and stabilized by using a unique three-dimensional network structure, and since cellulose nanofibers can be separated from light substances such as foods and organic resins, and further cellulose nanofibers at the separation site are dispersed in some inorganic substances or even metals, the range of use of cellulose nanofibers is extremely wide.
In the prior art, cellulose and polyvinylidene fluoride are sometimes mixed in different modes to prepare polyvinylidene fluoride with different characteristics, the hydrophobic characteristic of the polyvinylidene fluoride is improved by utilizing the organic group of the cellulose, but other characteristics of the organic group cannot be well utilized, and meanwhile, the functional characteristic of the polyvinylidene fluoride material cannot be enhanced.
Disclosure of Invention
In order to overcome the above defects of the prior art, embodiments of the present invention provide a method for preparing a nano-cellulose reinforced polyvinylidene fluoride composite material, so as to solve the problems.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a nano-cellulose reinforced polyvinylidene fluoride composite material specifically comprises the following steps:
step 10: preparing raw materials, namely preparing the following raw materials in parts by weight, wherein sufficient deionized water is used, 20-30 parts of cellulose nanofiber, 30-45 parts of PVDF monomer, 20-30 parts of cellulose nanocrystal, 3-5 parts of composite cellulase, 6-10 parts of modified cross-linking agent, 6-8 parts of dispersing agent, 4-8 parts of active agent, 2-5 parts of chain transfer agent, 5-10 parts of initiator, 3-5 parts of sepiolite fiber, 2-5 parts of shell powder, 3-5 parts of mineral refined talcum powder, 2-4 parts of flame retardant and 2-4 parts of composite stabilizer;
step 20: treating nano cellulose, performing enzymolysis on cellulose nano fiber, grinding cellulose nanocrystals into powdery solid with the fineness meeting the requirement, mixing the powdery solid with the powdery solid into a nano cellulose enzymolysis solution, and modifying and further dispersing the nano cellulose in the nano cellulose and the nano cellulose in the nano cellulose enzymolysis solution;
step 30: pre-treating a vinylidene fluoride monomer, adding 30-45 parts of the PVDF monomer prepared in the step 10, deionized water and 2-5 parts of an initiator into a reaction kettle B, and controlling the reaction kettle B to fully mix substances in the kettle to generate a modified vinylidene fluoride emulsion;
step 40: pretreating additives, namely adding 3-5 parts of sepiolite fibers, 2-5 parts of shell powder, 3-5 parts of mineral refined talcum powder, 2-4 parts of flame retardant and 2-4 parts of composite stabilizer prepared in the step 10 into a reaction kettle C for pretreatment to generate an additive suspension;
step 50: and (3) performing polymerization reaction, namely adding the nano-cellulose dispersion solution generated in the step (20) into a reaction kettle D, further continuously adding the modified vinylidene fluoride emulsion and the additive suspension generated in the step (40) into the reaction kettle D, controlling the temperature in the reaction kettle D to be 25-35 ℃, then continuously adding 2-5 parts of chain transfer agent into the reaction kettle D, performing polymerization reaction, and fully reacting for 3-4 hours to generate a final product in the reaction kettle D.
In a preferred embodiment, the specific operation steps in step 20 are as follows:
step 201: mechanically processing the nano-cellulose, namely adding 20-30 parts of the cellulose nano-crystals prepared in the step 10 into a grinder to obtain cellulose nano-crystal powder with the fineness of 500 meshes;
step 202: hydrolyzing nano-cellulose, preparing a reaction kettle A, adding sufficient deionized water into the reaction kettle A, then injecting 20-30 parts of cellulose nano-cellulose prepared in the step 10 into the reaction kettle A, then injecting 3-5 parts of composite cellulose into the reaction kettle A, keeping the temperature in the reaction kettle A at 25-35 ℃, performing enzymolysis, and performing full enzymolysis for 20-30 minutes to generate a nano-cellulose hydrolysis solution;
step 203: modifying nano-cellulose, namely injecting the cellulose nanocrystal powder generated in the step 201 into the reaction kettle A in the step 202 in a counterclockwise manner, controlling the temperature in the reaction kettle A to be 25-35 ℃, fully reacting for 15-25 minutes, continuously adding 6-10 parts of modified cross-linking agent into the reaction kettle A, and generating a nano-cellulose modified solution when the mixture in the reaction kettle A is viscous;
step 204: and (3) dispersing the nano-cellulose, injecting the nano-cellulose modified solution generated in the step 203 into a dispersion kettle, continuously adding 6-8 parts of dispersing agent into the dispersion kettle, controlling the temperature in the dispersion kettle to be 25-35 ℃, and controlling the dispersion kettle to stir anticlockwise for 45-60 minutes to generate the nano-cellulose dispersed solution.
In a preferred embodiment, in step 30:
step 301: blending raw materials, adding 30-45 parts of PVDF monomer and deionized water into a reaction kettle B, stirring for 20-30 minutes to uniformly mix the raw materials in the reaction kettle B, continuously adding 4-8 parts of an active agent into the reaction kettle B, controlling the temperature in the reaction kettle B to be 25-35 ℃, keeping the temperature for reacting for 35 minutes, and then fully reacting for 30-40 minutes;
step 302: and (3) modification, namely adding 2-5 parts of initiator into the reaction kettle B in the step 301, controlling the temperature in the reaction kettle B to be 30-40 ℃, and carrying out heat preservation and pressure maintaining reaction for 30-40 minutes to enable the reaction kettle B to be subjected to modification treatment to generate the modified vinylidene fluoride emulsion.
In a preferred embodiment, the modification treatment in step 302 is a chemical modification treatment of one or more of etherification, esterification and crosslinking.
In a preferred embodiment, the pretreatment step 40 comprises the following steps:
step 401: mechanically treating the additive, namely respectively grinding 3-5 parts of sepiolite fibers, 2-5 parts of shell powder and 3-5 parts of mineral refined talcum powder prepared in the step 10 by using a grinder, and respectively grinding the sepiolite fibers, the shell powder and the mineral refined talcum powder into powder meeting the fineness requirement;
step 402: preparing a pasty solution, uniformly mixing the sepiolite fibers, the shell powder and the mineral substance refined talcum powder in the step 401 into a reaction kettle C according to the ratio of 1:1:1, continuously adding sufficient deionized water into the reaction kettle C, and mixing the mixture in the reaction kettle C to ensure that the mixture in the reaction kettle C is uniformly mixed and pasty to generate the pasty solution;
step 403: and (3) continuously adding 2-4 parts of flame retardant and 2-4 parts of composite stabilizer into the pasty solution in the reaction kettle C to prepare suspension, and controlling the reaction kettle C to fully react to generate additive suspension.
In a preferred embodiment, the compound cellulase in the step 10 is one or a mixture of Endoglucanase (EG), exoglucanase (CBH) and cellobiase (BG).
In a preferred embodiment, the grinding rate of the grinder in step 201 is controlled to be 300-400r/min, and the grinding time is 40-60 minutes.
In a preferred embodiment, the fiber fineness of the sepiolite in the step 401 is controlled to be 400-450 meshes, the fineness of the shell powder is controlled to be 500-600 meshes, and the fineness of the mineral refining talcum powder is controlled to be 350-400 meshes.
In a preferred embodiment, the final product of step 50 is a viscous gel with a grainy feel on the surface;
in a preferred embodiment, in the step 403, the temperature in the reaction kettle C is controlled to be 25-35 ℃, the magnetic stirring reaction is kept for 3-4 hours, and then the ultrasonic treatment is carried out for 1-2 hours.
The invention has the technical effects and advantages that:
1. the invention takes vinylidene fluoride monomer metal inorganic matter and nano-cellulose material as base materials, connects the organic group on the nano-cellulose to the vinylidene fluoride monomer to form the vinylidene fluoride monomer with organic characteristic, then polymerizes the vinylidene fluoride monomer with organic characteristic into the polyvinylidene fluoride material, thereby enhancing the characteristic of the polyvinylidene fluoride, connecting the polyvinylidene fluoride compound containing the organic group with a plurality of organic groups, connecting metal particles by utilizing the network structure of the organic groups in water and stabilizing the metal particles, and further increasing the organic characteristic of the composite material on the basis of keeping the characteristic of the polyvinylidene fluoride compound, and simultaneously greatly improving the tensile strength of the material, the process is simple, the equipment requirement is low, and the operability is strong;
2. according to the invention, nano-cellulose is hydrolyzed and broken by cellulase, so that organic groups in cellulose are broken and dissociated in a solution, and then are combined with a polyvinylidene fluoride monomer to form the polyvinylidene fluoride monomer with organic functional characteristics, and further polymerized to form a composite material, and the polyvinylidene fluoride is enhanced by utilizing the organic characteristics of nano-cellulose.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment provides a preparation method of a nano-cellulose reinforced polyvinylidene fluoride composite material, which specifically comprises the following steps:
step 10: preparing raw materials, namely preparing 100 parts of deionized water, 20 parts of cellulose nano-fibers, 30 parts of PVDF monomers, 20 parts of cellulose nanocrystals, 3 parts of endoglucanase, 6 parts of a modified cross-linking agent, 6 parts of a dispersing agent, 4 parts of an active agent, 2 parts of a chain transfer agent, 5-10 parts of an initiator, 3 parts of sepiolite fibers, 2 parts of shell powder, 3 parts of mineral refined talcum powder, 2 parts of a flame retardant and 2 parts of a composite stabilizer;
step 20: the method comprises the following specific operation steps of nano-cellulose treatment:
step 201: mechanically processing the nano-cellulose, namely adding 20 parts of the cellulose nano-crystals prepared in the step 10 into a grinder, wherein the grinding speed of the grinder is controlled to be 300r/min, and the grinding time is 40 minutes, so as to obtain cellulose nano-crystal powder with the fineness of 500 meshes;
step 202: hydrolyzing nano-cellulose, preparing a reaction kettle A, adding 100 parts of deionized water into the reaction kettle A, then injecting 20 parts of cellulose nano-fiber prepared in the step 10 into the reaction kettle A, then injecting 3 parts of composite cellulose into the reaction kettle A, keeping the temperature in the reaction kettle A at 25 ℃, performing enzymolysis, and performing full enzymolysis for 20 minutes to generate a nano-cellulose hydrolysis solution;
step 203: modifying nano-cellulose, namely injecting the cellulose nanocrystal powder generated in the step 201 into the reaction kettle A in the step 202 in a counterclockwise manner, controlling the temperature in the reaction kettle A to be 25 ℃, fully reacting for 15 minutes, continuously adding 6 parts of modified cross-linking agent into the reaction kettle A, and generating a nano-cellulose modified solution when the mixture in the reaction kettle A is viscous;
step 204: dispersing the nano-cellulose, namely injecting the nano-cellulose modified solution generated in the step 203 into a dispersion kettle, continuously adding 6 parts of dispersing agent into the dispersion kettle, controlling the temperature in the dispersion kettle to be 25 ℃, and controlling the dispersion kettle to stir anticlockwise for 45 minutes to generate a nano-cellulose dispersed solution;
step 30: the vinylidene fluoride monomer is pretreated, the specific steps are as follows,
step 301: blending raw materials, adding 30 parts of PVDF monomer and deionized water into a reaction kettle B, stirring for 20 minutes to uniformly mix the raw materials in the reaction kettle B, continuously adding 4 parts of active agent into the reaction kettle B, controlling the temperature in the reaction kettle B to be 25 ℃, keeping the temperature, reacting for 35 minutes, and fully reacting for 30 minutes;
step 302: modifying, namely adding 2 parts of initiator into the reaction kettle B in the step 301, controlling the temperature in the reaction kettle B to be 30 ℃, and carrying out heat preservation and pressure maintaining reaction for 30 minutes to ensure that etherification modification occurs in the reaction kettle B to generate modified vinylidene fluoride emulsion;
step 40: additive pretreatment, which comprises the following specific steps:
step 401: mechanically processing the additives, namely respectively grinding 3 parts of sepiolite fibers, 2 parts of shell powder and 3 parts of mineral refined talcum powder prepared in the step 10 by using a grinder, respectively grinding the sepiolite fibers, the shell powder and the mineral refined talcum powder into powder meeting the fineness requirement, wherein the fineness of the sepiolite fibers is controlled to be 400 meshes, the fineness of the shell powder is controlled to be 500 meshes, and the fineness of the mineral refined talcum powder is controlled to be 350 meshes;
step 402: preparing a pasty solution, uniformly mixing the sepiolite fibers, the shell powder and the mineral substance refined talcum powder in the step 401 into a reaction kettle C according to the ratio of 1:1:1, continuously adding sufficient deionized water into the reaction kettle C, and mixing the mixture in the reaction kettle C to ensure that the mixture in the reaction kettle C is uniformly mixed and pasty to generate the pasty solution;
step 403: continuously adding 2 parts of flame retardant and 2 parts of composite stabilizer into the pasty solution in the reaction kettle C, controlling the reaction kettle C to perform full reaction, controlling the temperature in the reaction kettle C to be 25 ℃, performing heat preservation and magnetic stirring reaction for 3 hours, and performing ultrasonic treatment for 1 hour to generate an additive suspension;
step 50: and (3) performing polymerization reaction, namely adding the nano-cellulose dispersion solution generated in the step (20) into a reaction kettle D, further continuously adding the modified vinylidene fluoride emulsion and the additive suspension generated in the step (40) into the reaction kettle D, controlling the temperature in the reaction kettle D to be 25 ℃, then continuously adding 2 parts of chain transfer agent into the reaction kettle D, performing polymerization reaction, and fully reacting for 3 hours to generate a final product in the reaction kettle D, wherein the final product is viscous and colloidal, and the surface of the final product has granular feel.
Example 2:
the embodiment provides another preparation method of a nano-cellulose reinforced polyvinylidene fluoride composite material, which specifically comprises the following steps:
step 10: preparing raw materials, namely preparing the following raw materials in parts by weight, 125 parts of deionized water, 25 parts of cellulose nano-fibers, 35 parts of PVDF monomers, 25 parts of cellulose nanocrystals, 4 parts of exoglucanase, 8 parts of a modified cross-linking agent, 7 parts of a dispersing agent, 6 parts of an active agent, 3 parts of a chain transfer agent, 8 parts of an initiator, 4 parts of sepiolite fibers, 4 parts of shell powder, 4 parts of mineral refined talcum powder, 3 parts of a flame retardant and 3 parts of a composite stabilizer;
step 20: the method comprises the following specific operation steps of nano-cellulose treatment:
step 201: mechanically treating the nano-cellulose, namely adding 25 parts of the cellulose nano-crystals prepared in the step 10 into a grinder, wherein the grinding speed of the grinder is controlled to be 350r/min, and the grinding time is 50 minutes, so as to obtain cellulose nano-crystal powder with the fineness of 500 meshes;
step 202: hydrolyzing nano-cellulose, preparing a reaction kettle A, adding 125 parts of deionized water into the reaction kettle A, then injecting 25 parts of cellulose nano-fiber prepared in the step 10 into the reaction kettle A, then injecting 4 parts of composite cellulose into the reaction kettle A, keeping the temperature in the reaction kettle A at 30 ℃, performing enzymolysis, and performing full enzymolysis for 25 minutes to generate a nano-cellulose hydrolysis solution;
step 203: modifying nano-cellulose, namely injecting the cellulose nanocrystal powder generated in the step 201 into the reaction kettle A in the step 202 in a counterclockwise manner, controlling the temperature in the reaction kettle A to be 30 ℃, fully reacting for 20 minutes, continuously adding 8 parts of modified cross-linking agent into the reaction kettle A, and generating a nano-cellulose modified solution when the mixture in the reaction kettle A is viscous;
step 204: dispersing the nano-cellulose, namely injecting the nano-cellulose modified solution generated in the step 203 into a dispersion kettle, continuously adding 7 parts of dispersing agent into the dispersion kettle, controlling the temperature in the dispersion kettle to be 30 ℃, and controlling the dispersion kettle to stir anticlockwise for 50 minutes to generate a nano-cellulose dispersed solution;
step 30: the vinylidene fluoride monomer is pretreated, the specific steps are as follows,
step 301: blending raw materials, adding 35 parts of PVDF monomer and deionized water into a reaction kettle B, stirring for 25 minutes to uniformly mix the raw materials in the reaction kettle B, continuously adding 6 parts of active agent into the reaction kettle B, controlling the temperature in the reaction kettle B to be 30 ℃, keeping the temperature, reacting for 35 minutes, and fully reacting for 35 minutes;
step 302: modifying, namely adding 4 parts of initiator into the reaction kettle B in the step 301, controlling the temperature in the reaction kettle B to be 35 ℃, and carrying out heat preservation and pressure maintaining reaction for 35 minutes to ensure that esterification modification occurs in the reaction kettle B to generate modified vinylidene fluoride emulsion;
step 40: additive pretreatment, which comprises the following specific steps:
step 401: mechanically processing the additives, namely respectively grinding 4 parts of sepiolite fibers, 3 parts of shell powder and 4 parts of mineral refined talcum powder prepared in the step 10 by using a grinder, respectively grinding the sepiolite fibers, the shell powder and the mineral refined talcum powder into powder meeting the fineness requirement, wherein the fineness of the sepiolite fibers is controlled to be 420 meshes, the fineness of the shell powder is controlled to be 550 meshes, and the fineness of the mineral refined talcum powder is controlled to be 375 meshes;
step 402: preparing a pasty solution, uniformly mixing the sepiolite fibers, the shell powder and the mineral substance refined talcum powder in the step 401 into a reaction kettle C according to the ratio of 1:1:1, continuously adding sufficient deionized water into the reaction kettle C, and mixing the mixture in the reaction kettle C to ensure that the mixture in the reaction kettle C is uniformly mixed and pasty to generate the pasty solution;
step 403: continuously adding 3 parts of flame retardant and 3 parts of composite stabilizer into the pasty solution in the reaction kettle C, controlling the reaction kettle C to perform full reaction, controlling the temperature in the reaction kettle C to be 30 ℃, performing heat preservation and magnetic stirring reaction for 3.5 hours, and then performing ultrasonic treatment for 1.5 hours to generate an additive suspension;
step 50: and (3) performing polymerization reaction, namely adding the nano-cellulose dispersion solution generated in the step (20) into a reaction kettle D, further continuously adding the modified vinylidene fluoride emulsion and the additive suspension generated in the step (40) into the reaction kettle D, controlling the temperature in the reaction kettle D to be 30 ℃, then continuously adding 3 parts of chain transfer agent into the reaction kettle D, performing polymerization reaction, and fully reacting for 3.5 hours to generate a final product in the reaction kettle D, wherein the final product is viscous and colloidal, and the surface of the final product has granular feel.
Example 3:
the embodiment provides another preparation method of a nano-cellulose reinforced polyvinylidene fluoride composite material, which specifically comprises the following steps:
step 10: preparing raw materials, namely preparing 150 parts of deionized water, 30 parts of cellulose nano-fiber, 45 parts of PVDF monomer, 30 parts of cellulose nano-crystal, 5 parts of cellulose diglycosidase, 10 parts of modified cross-linking agent, 8 parts of dispersing agent, 8 parts of active agent, 5 parts of chain transfer agent, 10 parts of initiator, 5 parts of sepiolite fiber, 5 parts of shell powder, 5 parts of mineral refined talcum powder, 4 parts of flame retardant and 4 parts of composite stabilizer;
step 20: the method comprises the following specific operation steps of nano-cellulose treatment:
step 201: mechanically treating the nano-cellulose, namely adding 30 parts of the cellulose nano-crystals prepared in the step 10 into a grinder, wherein the grinding speed of the grinder is controlled to be 400r/min, and the grinding time is 60 minutes, so as to obtain cellulose nano-crystal powder with the fineness of 500 meshes;
step 202: hydrolyzing nano-cellulose, preparing a reaction kettle A, adding 150 parts of deionized water into the reaction kettle A, then injecting 30 parts of cellulose nano-fiber prepared in the step 10 into the reaction kettle A, then injecting 5 parts of composite cellulose into the reaction kettle A, keeping the temperature in the reaction kettle A at 35 ℃, performing enzymolysis, and performing full enzymolysis for 30 minutes to generate a nano-cellulose hydrolysis solution;
step 203: modifying nano-cellulose, namely injecting the cellulose nanocrystal powder generated in the step 201 into the reaction kettle A in the step 202 in a counterclockwise manner, controlling the temperature in the reaction kettle A to be 35 ℃, fully reacting for 25 minutes, continuously adding 10 parts of modified cross-linking agent into the reaction kettle A, and generating a nano-cellulose modified solution when the mixture in the reaction kettle A is viscous;
step 204: dispersing the nano-cellulose, namely injecting the nano-cellulose modified solution generated in the step 203 into a dispersion kettle, continuously adding 8 parts of dispersing agent into the dispersion kettle, controlling the temperature in the dispersion kettle to be 35 ℃, and controlling the dispersion kettle to stir anticlockwise for 60 minutes to generate a nano-cellulose dispersed solution;
step 30: the vinylidene fluoride monomer is pretreated, the specific steps are as follows,
step 301: blending raw materials, adding 45 parts of PVDF monomer and deionized water into a reaction kettle B, stirring for 30 minutes to uniformly mix the raw materials in the reaction kettle B, continuously adding 8 parts of an active agent into the reaction kettle B, controlling the temperature in the reaction kettle B to be 35 ℃, carrying out heat preservation reaction for 35 minutes, and then carrying out full reaction for 40 minutes;
step 302: modifying, namely adding 5 parts of initiator into the reaction kettle B in the step 301, controlling the temperature in the reaction kettle B to be 40 ℃, and carrying out heat preservation and pressure maintaining reaction for 40 minutes to ensure that chemical modification treatment of etherification and esterification composite is carried out in the reaction kettle B to generate modified vinylidene fluoride emulsion;
step 40: additive pretreatment, which comprises the following specific steps:
step 401: mechanically processing additives, namely grinding 5 parts of sepiolite fibers, 5 parts of shell powder and 5 parts of mineral refining talcum powder prepared in the step 10 respectively through a grinder, and grinding the sepiolite fibers, the shell powder and the mineral refining talcum powder respectively into powder meeting the fineness requirement, wherein the fineness of the sepiolite fibers is controlled to be 450 meshes, the fineness of the shell powder is controlled to be 600 meshes, and the fineness of the mineral refining talcum powder is controlled to be 400 meshes;
step 402: preparing a pasty solution, uniformly mixing the sepiolite fibers, the shell powder and the mineral substance refined talcum powder in the step 401 into a reaction kettle C according to the ratio of 1:1:1, continuously adding sufficient deionized water into the reaction kettle C, and mixing the mixture in the reaction kettle C to ensure that the mixture in the reaction kettle C is uniformly mixed and pasty to generate the pasty solution;
step 403: continuously adding 4 parts of flame retardant and 4 parts of composite stabilizer into the pasty solution in the reaction kettle C, controlling the reaction kettle C to perform full reaction, controlling the temperature in the reaction kettle C to be 35 ℃, performing heat preservation and magnetic stirring reaction for 4 hours, and performing ultrasonic treatment for 2 hours to generate an additive suspension;
step 50: and (3) performing polymerization reaction, namely adding the nano-cellulose dispersion solution generated in the step (20) into a reaction kettle D, further continuously adding the modified vinylidene fluoride emulsion and the additive suspension generated in the step (40) into the reaction kettle D, controlling the temperature in the reaction kettle D to be 35 ℃, then continuously adding 5 parts of chain transfer agent into the reaction kettle D, performing polymerization reaction, and fully reacting for 4 hours to generate a final product in the reaction kettle D, wherein the final product is viscous and colloidal, and the surface of the final product has granular feel.
Comparative example 1:
the embodiment specifically comprises the following steps:
step 10: preparing raw materials, namely preparing the following raw materials in parts by weight, 125 parts of deionized water, 35 parts of PVDF monomer, 8 parts of modified cross-linking agent, 7 parts of dispersing agent, 6 parts of active agent, 3 parts of chain transfer agent, 8 parts of initiator, 4 parts of sepiolite fiber, 4 parts of shell powder, 4 parts of mineral refined talcum powder, 3 parts of flame retardant and 3 parts of composite stabilizer;
step 20: the vinylidene fluoride monomer is pretreated, the specific steps are as follows,
step 201: blending raw materials, adding 35 parts of PVDF monomer and deionized water into a reaction kettle B, stirring for 25 minutes to uniformly mix the raw materials in the reaction kettle B, continuously adding 6 parts of active agent into the reaction kettle B, controlling the temperature in the reaction kettle B to be 30 ℃, keeping the temperature, reacting for 35 minutes, and fully reacting for 35 minutes;
step 202: modifying, namely adding 4 parts of initiator into the reaction kettle B in the step 301, controlling the temperature in the reaction kettle B to be 35 ℃, and carrying out heat preservation and pressure maintaining reaction for 35 minutes to ensure that esterification modification occurs in the reaction kettle B to generate modified vinylidene fluoride emulsion;
and step 30: additive pretreatment, which comprises the following specific steps:
step 301: mechanically processing additives, namely grinding 4 parts of sepiolite fibers, 3 parts of shell powder and 4 parts of mineral refining talcum powder prepared in the step 10 respectively through a grinder, and grinding the sepiolite fibers, the shell powder and the mineral refining talcum powder respectively into powder meeting the fineness requirement, wherein the fineness of the sepiolite fibers is controlled to be 420 meshes, the fineness of the shell powder is controlled to be 550 meshes, and the fineness of the mineral refining talcum powder is controlled to be 375 meshes;
step 302: preparing a pasty solution, uniformly mixing the sepiolite fibers, the shell powder and the mineral substance refined talcum powder in the step 401 into a reaction kettle C according to the ratio of 1:1:1, continuously adding sufficient deionized water into the reaction kettle C, and mixing the mixture in the reaction kettle C to ensure that the mixture in the reaction kettle C is uniformly mixed and pasty to generate the pasty solution;
step 303: continuously adding 3 parts of flame retardant and 3 parts of composite stabilizer into the pasty solution in the reaction kettle C, controlling the reaction kettle C to perform full reaction, controlling the temperature in the reaction kettle C to be 30 ℃, performing heat preservation and magnetic stirring reaction for 3.5 hours, and then performing ultrasonic treatment for 1.5 hours to generate an additive suspension;
step 40: and (3) performing polymerization reaction, namely adding the nano-cellulose dispersion solution generated in the step (20) into a reaction kettle D, further continuously adding the modified vinylidene fluoride emulsion and the additive suspension generated in the step (40) into the reaction kettle D, controlling the temperature in the reaction kettle D to be 30 ℃, then continuously adding 3 parts of chain transfer agent into the reaction kettle D, performing polymerization reaction, and fully reacting for 3.5 hours to generate a final product in the reaction kettle D, wherein the final product is viscous and colloidal, and the surface of the final product has granular feel.
Comparative example 2:
step 10: preparing raw materials, namely preparing the following raw materials in parts by weight, 125 parts of deionized water, 25 parts of cellulose nano-fiber, 35 parts of PVDF monomer, 25 parts of cellulose nano-crystal, 8 parts of modified cross-linking agent, 7 parts of dispersing agent, 6 parts of active agent, 3 parts of chain transfer agent, 8 parts of initiator, 4 parts of sepiolite fiber, 4 parts of shell powder, 4 parts of mineral refined talcum powder, 3 parts of flame retardant and 3 parts of composite stabilizer;
step 20: the method comprises the following specific operation steps of nano-cellulose treatment:
step 201: mechanically treating the nano-cellulose, namely adding 25 parts of the cellulose nano-crystals prepared in the step 10 into a grinder, wherein the grinding speed of the grinder is controlled to be 350r/min, and the grinding time is 50 minutes, so as to obtain cellulose nano-crystal powder with the fineness of 500 meshes;
step 202: modifying nano-cellulose, namely injecting the cellulose nanocrystal powder generated in the step 201 into a reaction kettle A in a counterclockwise manner, controlling the temperature in the reaction kettle A to be 30 ℃, fully reacting for 20 minutes, continuously adding 8 parts of modified cross-linking agent into the reaction kettle A, and generating a nano-cellulose modified solution when the mixture in the reaction kettle A is viscous;
step 203: dispersing the nano-cellulose, namely injecting the nano-cellulose modified solution generated in the step 203 into a dispersion kettle, continuously adding 7 parts of dispersing agent into the dispersion kettle, controlling the temperature in the dispersion kettle to be 30 ℃, and controlling the dispersion kettle to stir anticlockwise for 50 minutes to generate a nano-cellulose dispersed solution;
step 30: the vinylidene fluoride monomer is pretreated, the specific steps are as follows,
step 301: blending raw materials, adding 35 parts of PVDF monomer and deionized water into a reaction kettle B, stirring for 25 minutes to uniformly mix the raw materials in the reaction kettle B, continuously adding 6 parts of active agent into the reaction kettle B, controlling the temperature in the reaction kettle B to be 30 ℃, keeping the temperature, reacting for 35 minutes, and fully reacting for 35 minutes;
step 302: modifying, namely adding 4 parts of initiator into the reaction kettle B in the step 301, controlling the temperature in the reaction kettle B to be 35 ℃, and carrying out heat preservation and pressure maintaining reaction for 35 minutes to ensure that esterification modification occurs in the reaction kettle B to generate modified vinylidene fluoride emulsion;
step 40: additive pretreatment, which comprises the following specific steps:
step 401: mechanically processing the additives, namely respectively grinding 4 parts of sepiolite fibers, 3 parts of shell powder and 4 parts of mineral refined talcum powder prepared in the step 10 by using a grinder, respectively grinding the sepiolite fibers, the shell powder and the mineral refined talcum powder into powder meeting the fineness requirement, wherein the fineness of the sepiolite fibers is controlled to be 420 meshes, the fineness of the shell powder is controlled to be 550 meshes, and the fineness of the mineral refined talcum powder is controlled to be 375 meshes;
step 402: preparing a pasty solution, uniformly mixing the sepiolite fibers, the shell powder and the mineral substance refined talcum powder in the step 401 into a reaction kettle C according to the ratio of 1:1:1, continuously adding sufficient deionized water into the reaction kettle C, and mixing the mixture in the reaction kettle C to ensure that the mixture in the reaction kettle C is uniformly mixed and pasty to generate the pasty solution;
step 403: continuously adding 3 parts of flame retardant and 3 parts of composite stabilizer into the pasty solution in the reaction kettle C, controlling the reaction kettle C to perform full reaction, controlling the temperature in the reaction kettle C to be 30 ℃, performing heat preservation and magnetic stirring reaction for 3.5 hours, and then performing ultrasonic treatment for 1.5 hours to generate an additive suspension;
step 50: and (3) performing polymerization reaction, namely adding the nano-cellulose dispersion solution generated in the step (20) into a reaction kettle D, further continuously adding the modified vinylidene fluoride emulsion and the additive suspension generated in the step (40) into the reaction kettle D, controlling the temperature in the reaction kettle D to be 30 ℃, then continuously adding 3 parts of chain transfer agent into the reaction kettle D, performing polymerization reaction, and fully reacting for 3.5 hours to generate a final product in the reaction kettle D, wherein the final product is viscous and colloidal, and the surface of the final product has granular feel.
The composite materials obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to characteristic tests, which gave the following data:
| melt viscosity (mN/m) | Tensile strength | High temperature resistance | |
| Example 1 | 13.1 | 37.55 | 59 |
| Example 2 | 14.5 | 37.41 | 67 |
| Example 3 | 13.6 | 36.89 | 62 |
| Comparative example 1 | 7.7 | 65.37 | 45 |
| Comparative example 2 | 7.9 | 49.55 | 47 |
From the above data, it can be known that the composite material prepared in embodiment 2 of the present invention has the highest viscosity, the largest characteristic of tensile strength, and the strongest high temperature resistance, in the preparation process of the composite material, the vinylidene fluoride monomer, the metal inorganic substance, and the nano-cellulose material are used as the base materials, the organic group on the nano-cellulose is connected to the vinylidene fluoride monomer to form the vinylidene fluoride monomer with the organic characteristic, and then the vinylidene fluoride monomer with the organic characteristic is polymerized into the polyvinylidene fluoride material, so that the characteristic of the polyvinylidene fluoride is enhanced, the polyvinylidene fluoride composite is connected with a plurality of organic groups, the network structure of the organic groups in water is used to connect the metal particles and stabilize the metal particles, and the composite material formed by the method further increases the organic characteristic on the basis of maintaining the characteristic of the polyvinylidene fluoride compound, meanwhile, the tensile strength of the material is greatly improved, the process is simple, the equipment requirement is low, and the operability is strong.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a nano-cellulose reinforced polyvinylidene fluoride composite material is characterized by comprising the following steps: the method specifically comprises the following steps:
step 10: preparing raw materials, namely preparing the following raw materials in parts by weight, wherein sufficient deionized water is used, 20-30 parts of cellulose nanofiber, 30-45 parts of PVDF monomer, 20-30 parts of cellulose nanocrystal, 3-5 parts of composite cellulase, 6-10 parts of modified cross-linking agent, 6-8 parts of dispersing agent, 4-8 parts of active agent, 2-5 parts of chain transfer agent, 5-10 parts of initiator, 3-5 parts of sepiolite fiber, 2-5 parts of shell powder, 3-5 parts of mineral refined talcum powder, 2-4 parts of flame retardant and 2-4 parts of composite stabilizer;
step 20: treating nano cellulose, performing enzymolysis on cellulose nano fiber, grinding cellulose nanocrystals into powdery solid with the fineness meeting the requirement, mixing the powdery solid with the powdery solid into a nano cellulose enzymolysis solution, and modifying and further dispersing the nano cellulose in the nano cellulose and the nano cellulose in the nano cellulose enzymolysis solution;
step 30: pre-treating a vinylidene fluoride monomer, adding 30-45 parts of the PVDF monomer prepared in the step 10, deionized water and 2-5 parts of an initiator into a reaction kettle B, and controlling the reaction kettle B to fully mix substances in the kettle to generate a modified vinylidene fluoride emulsion;
step 40: pretreating additives, namely adding 3-5 parts of sepiolite fibers, 2-5 parts of shell powder, 3-5 parts of mineral refined talcum powder, 2-4 parts of flame retardant and 2-4 parts of composite stabilizer prepared in the step 10 into a reaction kettle C for pretreatment to generate an additive suspension;
step 50: and (3) performing polymerization reaction, namely adding the nano-cellulose dispersion solution generated in the step (20) into a reaction kettle D, further continuously adding the modified vinylidene fluoride emulsion and the additive suspension generated in the step (40) into the reaction kettle D, controlling the temperature in the reaction kettle D to be 25-35 ℃, then continuously adding 2-5 parts of chain transfer agent into the reaction kettle D, performing polymerization reaction, and fully reacting for 3-4 hours to generate a final product in the reaction kettle D.
2. The method of preparing a nano-cellulose reinforced polyvinylidene fluoride composite material according to claim 1, wherein: the specific operation steps in the step 20 are as follows:
step 201: mechanically processing the nano-cellulose, namely adding 20-30 parts of the cellulose nano-crystals prepared in the step 10 into a grinder to obtain cellulose nano-crystal powder with the fineness of 500 meshes;
step 202: hydrolyzing nano-cellulose, preparing a reaction kettle A, adding sufficient deionized water into the reaction kettle A, then injecting 20-30 parts of cellulose nano-cellulose prepared in the step 10 into the reaction kettle A, then injecting 3-5 parts of composite cellulose into the reaction kettle A, keeping the temperature in the reaction kettle A at 25-35 ℃, performing enzymolysis, and performing full enzymolysis for 20-30 minutes to generate a nano-cellulose hydrolysis solution;
step 203: modifying nano-cellulose, namely injecting the cellulose nanocrystal powder generated in the step 201 into the reaction kettle A in the step 202 in a counterclockwise manner, controlling the temperature in the reaction kettle A to be 25-35 ℃, fully reacting for 15-25 minutes, continuously adding 6-10 parts of modified cross-linking agent into the reaction kettle A, and generating a nano-cellulose modified solution when the mixture in the reaction kettle A is viscous;
step 204: and (3) dispersing the nano-cellulose, injecting the nano-cellulose modified solution generated in the step 203 into a dispersion kettle, continuously adding 6-8 parts of dispersing agent into the dispersion kettle, controlling the temperature in the dispersion kettle to be 25-35 ℃, and controlling the dispersion kettle to stir anticlockwise for 45-60 minutes to generate the nano-cellulose dispersed solution.
3. The method of preparing a nano-cellulose reinforced polyvinylidene fluoride composite material according to claim 1, wherein: in the step 30:
step 301: blending raw materials, adding 30-45 parts of PVDF monomer and deionized water into a reaction kettle B, stirring for 20-30 minutes to uniformly mix the raw materials in the reaction kettle B, continuously adding 4-8 parts of an active agent into the reaction kettle B, controlling the temperature in the reaction kettle B to be 25-35 ℃, keeping the temperature for reacting for 35 minutes, and then fully reacting for 30-40 minutes;
step 302: and (3) modification, namely adding 2-5 parts of initiator into the reaction kettle B in the step 301, controlling the temperature in the reaction kettle B to be 30-40 ℃, and carrying out heat preservation and pressure maintaining reaction for 30-40 minutes to enable the reaction kettle B to be subjected to modification treatment to generate the modified vinylidene fluoride emulsion.
4. The method for preparing a nano-cellulose reinforced polyvinylidene fluoride composite material according to claim 3, wherein the method comprises the following steps: the modification treatment in the step 302 is one or more of chemical modification treatment of etherification, esterification and crosslinking.
5. The method of preparing a nano-cellulose reinforced polyvinylidene fluoride composite material according to claim 1, wherein: the pretreatment of the additives in the step 40 comprises the following specific steps:
step 401: mechanically treating the additive, namely respectively grinding 3-5 parts of sepiolite fibers, 2-5 parts of shell powder and 3-5 parts of mineral refined talcum powder prepared in the step 10 by using a grinder, and respectively grinding the sepiolite fibers, the shell powder and the mineral refined talcum powder into powder meeting the fineness requirement;
step 402: preparing a pasty solution, uniformly mixing the sepiolite fibers, the shell powder and the mineral substance refined talcum powder in the step 401 into a reaction kettle C according to the proportion of 1:1:1, continuously adding sufficient deionized water into the reaction kettle C, and mixing the mixture in the reaction kettle C to ensure that the mixture in the reaction kettle C is uniformly mixed and pasty to generate a pasty solution;
step 403: and (3) continuously adding 2-4 parts of flame retardant and 2-4 parts of composite stabilizer into the pasty solution in the reaction kettle C to prepare suspension, and controlling the reaction kettle C to fully react to generate additive suspension.
6. The method of preparing a nano-cellulose reinforced polyvinylidene fluoride composite material according to claim 1, wherein: the compound cellulase in the step 10 is one or a mixture of more of Endoglucanase (EG), exoglucanase (CBH) and cellulose diglycosidase (BG).
7. The method for preparing a nano-cellulose reinforced polyvinylidene fluoride composite material according to claim 2, wherein the method comprises the following steps: the grinding rate of the grinder in the step 201 is controlled to be 300-400r/min, and the grinding time is 40-60 minutes.
8. The method for preparing a nano-cellulose reinforced polyvinylidene fluoride composite material according to claim 5, wherein the method comprises the following steps: in the step 401, the fiber fineness of the sepiolite is controlled to be 450 meshes, the fineness of the shell powder is controlled to be 600 meshes, and the fineness of the mineral refining talcum powder is controlled to be 400 meshes.
9. The method of preparing a nano-cellulose reinforced polyvinylidene fluoride composite material according to claim 1, wherein: the final product of step 50 appears as a viscous gel with a grainy surface.
10. The method of preparing a nano-cellulose reinforced polyvinylidene fluoride composite material according to claim 1, wherein: in the step 403, the temperature in the reaction kettle C is controlled to be 25-35 ℃, the magnetic stirring reaction is carried out for 3-4 hours under the condition of heat preservation, and then ultrasonic treatment is carried out for 1-2 hours.
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