CN111303514A - Preparation method of high-stability oxygen-barrier pipe - Google Patents
Preparation method of high-stability oxygen-barrier pipe Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08L23/04—Homopolymers or copolymers of ethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2023/00—Tubular articles
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Abstract
The invention discloses a preparation method of a high-stability oxygen-resistant pipe, which comprises the following steps: firstly, preparing a polyvinyl alcohol/nano cellulose composite material; secondly, preparing polyvinyl alcohol/nano-cellulose/graphene polymer; and thirdly, preparing the high-stability oxygen-resistant pipe. The composite pipe prepared by the invention has better oxygen resistance and stability, and can be applied to heat-insulating pipes of floor heating systems.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of oxygen resistance of high polymer materials, in particular to a preparation method of a high-stability oxygen-resistant pipe.
[ background of the invention ]
In a floor heating system, the requirement of a pipe for blocking oxygen is high, at present, most of PE-X or PE-RT pipes are coated or co-extruded with one layer of EVOH (polyethylene-vinyl alcohol) at home, and the EVOH has the gas blocking effect, but due to the existence of hydroxyl in the molecular structure of the EVOH resin, the EVOH resin has hydrophilicity and hygroscopicity. After moisture is adsorbed, the gas barrier property is not much different from that of PE-X, when the gas barrier layer is used in a floor heating pipeline, the so-called barrier layer can absorb moisture in concrete and completely lose oxygen barrier capability, and the permeability coefficient of the PE gas pipeline on the existing market to oxygen is high.
At present, the production and processing method of the oxygen-barrier plastic pipe mostly adopts a coating method, the method is 2-step forming, namely, an adhesive layer and a barrier layer (EVOH) coating are simultaneously extruded on a single-layer pipe which is extruded and shaped to form a three-layer structure, but the adhesive strength of the co-extrusion surface is low, and the delamination phenomenon is easy to generate.
Chinese patent 106700110A discloses a preparation method of a graphene oxide/nano-cellulose/polyvinyl alcohol composite film, which solves the problem of poor barrier property of the composite film, and in experimental research, the oxygen resistance of the composite film is improved by compounding three materials of polyvinyl alcohol/nano-cellulose/graphene oxide with a polyethylene material to form a pipe, but the graphene oxide is rich in oxidation state groups on the surface and can chemically react with a product due to excessive activity in the preparation process of the pipe to cause deterioration, so that the composite pipe loses the excellent performance of the graphene and is poor in stability.
[ summary of the invention ]
One of the purposes of the invention is to provide a one-step co-extruded multi-core pipe material, which solves the problem of layering in the background technology;
the second purpose of the invention is to provide a polyvinyl alcohol/nano-cellulose/graphene composite pipe with good stability, which solves the problem that the pipe is denatured due to excessive activity of graphene oxide;
the invention further aims to provide the polyvinyl alcohol/nano-cellulose/graphene composite pipe with good oxygen resistance, which meets the requirement on the oxygen resistance when the polyvinyl alcohol/nano-cellulose/graphene composite pipe is used in a floor heating system.
In order to solve the technical problems, the invention adopts the technical scheme that:
the method is characterized in that the high strength and high length-diameter ratio of biomass nano-cellulose fibers (CNF) are utilized, nano-cellulose is introduced into polyvinyl alcohol (PVA), and reduced graphene oxide (rGO) is selected as a reinforcing phase. The method comprises the steps of simultaneously introducing nano-cellulose and graphene oxide into a polyvinyl alcohol matrix, and carrying out in-situ reduction on the graphene oxide by using a green reducing agent D-fructose to obtain rGO. The polyvinyl alcohol/nano-cellulose/graphene (PVA/CNF/rGO) composite polymer material with excellent mechanical property and barrier property is prepared by adopting a casting method. And finally, adding the composite polymer material into heat-resistant polyethylene according to a certain proportion to perform pipe extrusion molding to obtain the high-stability oxygen-resistant pipe.
Specifically, the preparation steps of the polyvinyl alcohol/nano-cellulose/graphene composite polymer are as follows:
1. preparation of nano-cellulose suspension and graphene oxide solution
Preparing nano-cellulose by adopting bamboo powder and graphene oxide by adopting graphite powder, extracting the nano-cellulose from the bamboo powder by utilizing chemical treatment and mechanical treatment, and preparing nano-cellulose suspension with the mass fraction of 0.8%. An improved Hummers method is adopted to prepare the graphene oxide aqueous solution with the mass concentration of 0.5 mg/mL.
Preferably, the bamboo powder has a particle size of 40-60 meshes.
2. Preparation of polyvinyl alcohol/nano cellulose composite material
Dissolving polyvinyl alcohol particles in distilled water, stirring for 2h at a certain temperature to obtain a polyvinyl alcohol solution, and standing to remove bubbles for later use. And pouring 50ml to 200ml of polyvinyl alcohol aqueous solution on a glass substrate, drying at room temperature, and grinding into powder.
Mixing the nano-cellulose solution with polyvinyl alcohol, wherein the solute nano-cellulose accounts for 10% of the mass of the polyvinyl alcohol. The mixed solution was stirred for 1h under magnetic stirring and then sonicated. And standing for 24 hours, pouring the mixture into a glass substrate, drying the mixture at room temperature, and grinding the mixture into powder to obtain the polyvinyl alcohol/nano cellulose composite material.
Preferably, the stirring temperature employed is from 80 to 100 ℃.
3. Preparation of polyvinyl alcohol/nano-cellulose/graphene polymer
Respectively taking graphene oxide and polyvinyl alcohol/nano-cellulose with the mass ratio of (1-5):5, dropwise adding the graphene oxide aqueous solution to the polyvinyl alcohol/nano-cellulose mixed solution, and gently stirring by using a mechanical stirrer. The green reducing agent D-fructose was added and the pH of the solution was adjusted to alkaline. And then placing the mixture in a water bath at 95 ℃ for reaction for 2 hours, and then carrying out ultrasonic treatment to obtain a polyvinyl alcohol/nano-cellulose/graphene mixed solution. And standing for 24 hours, pouring the mixture on a glass substrate, drying at room temperature, uncovering the film, and crushing into powder to obtain the polyvinyl alcohol/nano-cellulose/graphene composite material.
Preferably, the mass ratio of the D-fructose to the graphene oxide is (10-5): 1.
preferably, the pH of the solution is adjusted with aqueous ammonia.
Preferably the pH is adjusted to 8-9.
4. Preparation of high-stability oxygen-barrier pipe
And (3) mixing the polyvinyl alcohol/nano-cellulose/graphene polymer obtained in the step (3) with heat-resistant polyethylene, color master batch, antioxidant and polyphthalamide, and then co-extruding to obtain the modified graphene oxide oxygen barrier pipe.
Wherein the antioxidant is 2, 8-di-tert-butyl 4-methylphenol and pentaerythritol phosphite ester, and the mass ratio is 1: 0.1; the mass ratio of the polyvinyl alcohol/nano-cellulose/graphene polymer to the heat-resistant polyethylene, the color master batch, the antioxidant and the polyphthalamide is (1-2.5): 100:1.5:1:1.5.
Further, the co-extrusion process comprises the following steps: the premix is prepared by melt blending extrusion of a twin-screw extruder, wherein the extrusion temperature of a first section is 190 ℃, the extrusion temperature of a second section is 200 ℃, the extrusion temperature of a third section is 195 ℃, the extrusion temperature of a fourth section is 200 ℃, the die head temperature of the first section is 200 ℃, the die head temperature of the second section is 220 ℃, the die head temperature of the third section is 230 ℃, the die head temperature of the fourth section is 220 ℃, the die head temperature of a fifth section is 200 ℃, the vacuum degree is 0.03MPa, the torque current is 80A, and the screw rotation speed is 105 rpm; and cooling and cutting to obtain the high-stability oxygen-barrier pipe.
The invention has the beneficial effects that:
1) the method is characterized in that the high strength and high length-diameter ratio of the biomass nano-cellulose fiber (CNF) are utilized, nano-cellulose is introduced into polyvinyl alcohol (PVA), and reduced graphene oxide (rGO) is selected as a reinforcing phase to improve the oxygen resistance of the composite material.
2) The graphene oxide is reduced through chemical reaction, and the purpose is to thoroughly remove the attached oxide group on the graphene oxide, so that the structure of the graphene oxide is stable, the prepared product is ensured not to deteriorate due to chemical reaction caused by excessive activity, and meanwhile, the excellent performance of the graphene is also kept. The stability of the composite material is ensured.
3) The polyvinyl alcohol/nano-cellulose/graphene polymer is added into the heat-resistant polyethylene according to a certain proportion for pipe extrusion molding, so that the phenomenon that layering is easy to generate due to low bonding strength in a coating method is avoided, and the process of adding the three materials into PE for extrusion relates to chemical grafting reaction to form the high-stability oxygen-resistant composite pipe.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantageous effects of the present invention more apparent, the present invention is further described in detail with reference to the following detailed description. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example one
S1, preparing a nano-cellulose suspension and a graphene oxide solution
Preparing nano-cellulose by adopting bamboo powder and graphene oxide by adopting graphite powder, extracting the nano-cellulose from the bamboo powder with the particle size of 40 meshes by utilizing chemical treatment, and preparing nano-cellulose suspension with the mass fraction of 0.8%. An improved Hummers method is adopted to prepare the graphene oxide aqueous solution with the mass concentration of 0.5 mg/mL.
S2, preparation of polyvinyl alcohol/nano-cellulose composite material
Dissolving polyvinyl alcohol particles in distilled water with a specific volume, stirring for 2 hours at 80 ℃ to obtain a polyvinyl alcohol solution, and standing to remove bubbles for later use. And then 50ml of polyvinyl alcohol aqueous solution is poured on a glass substrate, dried at room temperature and ground into powder. Mixing the nano-cellulose with a polyvinyl alcohol solution, wherein the nano-cellulose in the solute of the mixed solution accounts for 10% of the mass of the polyvinyl alcohol. Stirring the mixed solution for 1h under magnetic stirring, performing ultrasonic treatment, standing for 24h, pouring into a glass substrate, drying at room temperature, and grinding into powder to obtain the polyvinyl alcohol/nano cellulose composite material.
S3, preparing polyvinyl alcohol/nano-cellulose/graphene polymer
Taking graphene oxide and polyvinyl alcohol/nano-cellulose in a mass ratio of 1:5, dropwise adding the graphene oxide aqueous solution to the polyvinyl alcohol/nano-cellulose mixed solution, and slightly stirring by using a mechanical stirrer. Adding a green reducing agent D-fructose, wherein the mass ratio of the reducing agent to the graphene oxide is 5:1, and adjusting the pH of the solution to 8 by using ammonia water. And then placing the mixture in a water bath at 95 ℃ for reaction for 2h, and then carrying out ultrasonic treatment for 5min to obtain a polyvinyl alcohol/nano-cellulose/graphene mixed solution. And standing for 24 hours, pouring the mixture on a glass substrate, drying at room temperature, uncovering the film, and crushing into powder to obtain the polyvinyl alcohol/nano-cellulose/graphene composite material.
S4, preparing high-stability oxygen-resistant pipe
Taking 100 parts of heat-resistant polyethylene, 1.5 parts of color master batch, 1 part of antioxidant (the antioxidant comprises a main antioxidant and an auxiliary antioxidant in a mass ratio of 1: 0.1, the main antioxidant is 2, 8-di-tert-butyl 4-methylphenol, the auxiliary antioxidant is pentaerythritol phosphite), 1.5 parts of PPA and 1.0 part of polyvinyl alcohol/nano-cellulose/graphene polymer, uniformly mixing in a mixer to obtain a premix, wherein the premix is prepared by melting, blending and extruding by a double-screw extruder, the first-stage extrusion temperature is 190 ℃, the second-stage extrusion temperature is 200 ℃, the third-stage extrusion temperature is 195 ℃, the fourth-stage extrusion temperature is 200 ℃, the first-stage die head temperature is 200 ℃, the second-stage die head temperature is 220 ℃, the third-stage die head temperature is 230 ℃, the fourth-stage die head temperature is 220 ℃, the fifth-stage die head temperature is 200 ℃, the vacuum degree is 0.03MPa, and the torque current is 80A, screw speed 105 rpm; and cooling and cutting to obtain the high-stability oxygen-resistant pipe.
Example two
S5, preparing a nano-cellulose suspension and a graphene oxide solution
Preparing nano-cellulose by adopting bamboo powder and graphene oxide by adopting graphite powder, extracting the nano-cellulose from the bamboo powder with the particle size of 50 meshes by utilizing chemical treatment, and preparing nano-cellulose suspension with the mass fraction of 0.8%. An improved Hummers method is adopted to prepare the graphene oxide aqueous solution with the mass concentration of 0.5 mg/mL.
S6, preparation of polyvinyl alcohol/nano-cellulose composite material
Dissolving polyvinyl alcohol particles in distilled water with a specific volume, stirring for 2 hours at 80 ℃ to obtain a polyvinyl alcohol solution, and standing to remove bubbles for later use. And then pouring 50ml of polyvinyl alcohol aqueous solution, injecting the polyvinyl alcohol aqueous solution into a glass substrate, drying the glass substrate at room temperature, and grinding the glass substrate into powder. Mixing the nano-cellulose with a polyvinyl alcohol solution, wherein the solute nano-cellulose in the mixed solution accounts for 10% of the mass of the polyvinyl alcohol. Stirring the mixed solution for 1h under magnetic stirring, performing ultrasonic treatment, standing for 24h, pouring into a glass substrate, drying at room temperature, and grinding into powder to obtain the polyvinyl alcohol/nano cellulose composite material.
S7, preparation of polyvinyl alcohol/nano-cellulose/graphene polymer
Taking graphene oxide and polyvinyl alcohol/nano-cellulose in a mass ratio of 2:5, dropwise adding the graphene oxide aqueous solution to the polyvinyl alcohol/nano-cellulose mixed solution, and slightly stirring by using a mechanical stirrer. Adding a green reducing agent D-fructose, wherein the mass ratio of the reducing agent to the graphene oxide is 6:1, and adjusting the pH of the solution to 8.5 by using ammonia water. And then placing the mixture in a water bath at 95 ℃ for reaction for 2h, and then carrying out ultrasonic treatment for 5min to obtain a polyvinyl alcohol/nano-cellulose/graphene mixed solution. And standing for 24 hours, pouring the mixture on a glass substrate, drying at room temperature, uncovering the film, and crushing into powder to obtain the polyvinyl alcohol/nano-cellulose/graphene composite material.
S8, preparing high-stability oxygen-resistant pipe
Taking 100 parts of heat-resistant polyethylene, 1.5 parts of color master batch, 1 part of antioxidant (the antioxidant comprises a main antioxidant and an auxiliary antioxidant in a mass ratio of 1: 0.1, the main antioxidant is 2, 8-di-tert-butyl 4-methylphenol, the auxiliary antioxidant is pentaerythritol phosphite), 1.5 parts of PPA and 2.0 parts of polyvinyl alcohol/nano-cellulose/graphene polymer, uniformly mixing in a mixer to obtain a premix, wherein the premix is prepared by melting, blending and extruding by a double-screw extruder, the first-stage extrusion temperature is 190 ℃, the second-stage extrusion temperature is 200 ℃, the third-stage extrusion temperature is 195 ℃, the fourth-stage extrusion temperature is 200 ℃, the first-stage die head temperature is 200 ℃, the second-stage die head temperature is 220 ℃, the third-stage die head temperature is 230 ℃, the fourth-stage die head temperature is 220 ℃, the fifth-stage die head temperature is 200 ℃, the vacuum degree is 0.03MPa, and the torque current is 80A, screw speed 105 rpm; and cooling and cutting to obtain the high-stability oxygen-resistant pipe.
EXAMPLE III
S9, preparing a nano-cellulose suspension and a graphene oxide solution
Preparing nano-cellulose by adopting bamboo powder and graphene oxide by adopting graphite powder, extracting the nano-cellulose from the bamboo powder with the particle size of 60 meshes by utilizing chemical treatment, and preparing nano-cellulose suspension with the mass fraction of 0.8%. An improved Hummers method is adopted to prepare the graphene oxide aqueous solution with the mass concentration of 0.5 mg/mL.
S10, preparation of polyvinyl alcohol/nano-cellulose composite material
Dissolving polyvinyl alcohol particles in distilled water with a specific volume, stirring for 2 hours at 90 ℃ to obtain a polyvinyl alcohol solution, and standing to remove bubbles for later use. Then pouring 100ml of a certain amount of polyvinyl alcohol aqueous solution on a glass substrate, drying at room temperature, and grinding into powder. Mixing the nano-cellulose with a polyvinyl alcohol solution, wherein the nano-cellulose in the solute of the mixed solution accounts for 10% of the mass of the polyvinyl alcohol. Stirring the mixed solution for 1h under magnetic stirring, performing ultrasonic treatment, standing for 24h, pouring into a glass substrate, drying at room temperature, and grinding into powder to obtain the polyvinyl alcohol/nano cellulose composite material.
S11, preparation of polyvinyl alcohol/nano-cellulose/graphene polymer
Taking graphene oxide and polyvinyl alcohol/nano-cellulose in a mass ratio of 3:5, dropwise adding the graphene oxide aqueous solution to the polyvinyl alcohol/nano-cellulose mixed solution, and slightly stirring by using a mechanical stirrer. Adding a green reducing agent D-fructose, wherein the mass ratio of the reducing agent to the graphene oxide is 7:1, and adjusting the pH of the solution to 9 by using ammonia water. And then placing the mixture in a water bath at 95 ℃ for reaction for 2h, and then carrying out ultrasonic treatment for 5min to obtain a polyvinyl alcohol/nano-cellulose/graphene mixed solution. And standing for 24 hours, pouring the mixture on a glass substrate, drying at room temperature, uncovering the film, and crushing into powder to obtain the polyvinyl alcohol/nano-cellulose/graphene composite material.
S12, preparation of high-stability oxygen-resistant pipe
Taking 100 parts of heat-resistant polyethylene, 1.5 parts of color master batch, 1 part of antioxidant (the antioxidant comprises a main antioxidant and an auxiliary antioxidant in a mass ratio of 1: 0.1, the main antioxidant is 2, 8-di-tert-butyl 4-methylphenol, the auxiliary antioxidant is pentaerythritol phosphite), 1.5 parts of PPA and 2.0 parts of polyvinyl alcohol/nano-cellulose/graphene polymer, uniformly mixing in a mixer to obtain a premix, wherein the premix is prepared by melting, blending and extruding by a double-screw extruder, the first-stage extrusion temperature is 190 ℃, the second-stage extrusion temperature is 200 ℃, the third-stage extrusion temperature is 195 ℃, the fourth-stage extrusion temperature is 200 ℃, the first-stage die head temperature is 200 ℃, the second-stage die head temperature is 220 ℃, the third-stage die head temperature is 230 ℃, the fourth-stage die head temperature is 220 ℃, the fifth-stage die head temperature is 200 ℃, the vacuum degree is 0.03MPa, and the torque current is 80A, screw speed 105 rpm; and cooling and cutting to obtain the high-stability oxygen-resistant pipe.
Example four
S13, preparing a nano-cellulose suspension and a graphene oxide solution
Preparing nano-cellulose by adopting bamboo powder and graphene oxide by adopting graphite powder, extracting the nano-cellulose from the bamboo powder with the particle size of 40 meshes by utilizing chemical treatment, and preparing nano-cellulose suspension with the mass fraction of 0.8%. An improved Hummers method is adopted to prepare the graphene oxide aqueous solution with the mass concentration of 0.5 mg/mL.
S14, preparation of polyvinyl alcohol/nano-cellulose composite material
Dissolving polyvinyl alcohol particles in distilled water with a specific volume, stirring for 2 hours at 90 ℃ to obtain a polyvinyl alcohol solution, and standing to remove bubbles for later use. Then pouring 100ml of a certain amount of polyvinyl alcohol aqueous solution on a glass substrate, drying at room temperature, and grinding into powder. Mixing the nano-cellulose with a polyvinyl alcohol solution, wherein the nano-cellulose in the solute of the mixed solution accounts for 10% of the mass of the polyvinyl alcohol. Stirring the mixed solution for 1h under magnetic stirring, performing ultrasonic treatment, standing for 24h, pouring into a glass substrate, drying at room temperature, and grinding into powder to obtain the polyvinyl alcohol/nano cellulose composite material.
S15, preparation of polyvinyl alcohol/nano-cellulose/graphene polymer
Taking graphene oxide and polyvinyl alcohol/nano-cellulose in a mass ratio of 4:5, dropwise adding the graphene oxide aqueous solution to the polyvinyl alcohol/nano-cellulose mixed solution, and slightly stirring by using a mechanical stirrer. Adding a green reducing agent D-fructose, wherein the mass ratio of the reducing agent to the graphene oxide is 8:1, and adjusting the pH of the solution to 9 by using ammonia water. And then placing the mixture in a water bath at 95 ℃ for reaction for 2h, and then carrying out ultrasonic treatment for 5min to obtain a polyvinyl alcohol/nano-cellulose/graphene mixed solution. And standing for 24 hours, pouring the mixture on a glass substrate, drying at room temperature, uncovering the film, and crushing into powder to obtain the polyvinyl alcohol/nano-cellulose/graphene composite material.
S16. preparation of high-stability oxygen-resistant pipe
Taking 100 parts of heat-resistant polyethylene, 1.5 parts of color master batch, 1 part of antioxidant (the antioxidant comprises a main antioxidant and an auxiliary antioxidant in a mass ratio of 1: 0.1, the main antioxidant is 2, 8-di-tert-butyl 4-methylphenol, the auxiliary antioxidant is pentaerythritol phosphite), 1.5 parts of PPA and 2.5 parts of polyvinyl alcohol/nano-cellulose/graphene polymer, uniformly mixing in a mixer to obtain a premix, wherein the premix is prepared by melting, blending and extruding by a double-screw extruder, the first-stage extrusion temperature is 190 ℃, the second-stage extrusion temperature is 200 ℃, the third-stage extrusion temperature is 195 ℃, the fourth-stage extrusion temperature is 200 ℃, the first-stage die head temperature is 200 ℃, the second-stage die head temperature is 220 ℃, the third-stage die head temperature is 230 ℃, the fourth-stage die head temperature is 220 ℃, the fifth-stage die head temperature is 200 ℃, the vacuum degree is 0.03MPa, and the torque current is 80A, screw speed 105 rpm; and cooling and cutting to obtain the high-stability oxygen-resistant pipe.
EXAMPLE five
S17, preparing a nano-cellulose suspension and a graphene oxide solution
Preparing nano-cellulose by adopting bamboo powder and graphene oxide by adopting graphite powder, extracting the nano-cellulose from the bamboo powder with the particle size of 40 meshes by utilizing chemical treatment, and preparing nano-cellulose suspension with the mass fraction of 0.8%. An improved Hummers method is adopted to prepare the graphene oxide aqueous solution with the mass concentration of 0.5 mg/mL.
S18, preparation of polyvinyl alcohol/nano-cellulose composite material
Dissolving polyvinyl alcohol particles in distilled water with a specific volume, stirring for 2 hours at 100 ℃ to obtain a polyvinyl alcohol solution, and standing to remove bubbles for later use. Then pouring 100ml of a certain amount of polyvinyl alcohol aqueous solution on a glass substrate, drying at room temperature, and grinding into powder. Mixing the nano-cellulose with a polyvinyl alcohol solution, wherein the nano-cellulose in the solute of the mixed solution accounts for 10% of the mass of the polyvinyl alcohol. Stirring the mixed solution for 1h under magnetic stirring, performing ultrasonic treatment for 30min, standing for 24h, pouring the mixed solution into a glass substrate, drying at room temperature, and grinding into powder to obtain the polyvinyl alcohol/nano cellulose composite material.
S19, preparation of polyvinyl alcohol/nano-cellulose/graphene polymer
Taking graphene oxide and polyvinyl alcohol/nano-cellulose in a mass ratio of 1:1, dropwise adding the graphene oxide aqueous solution to the polyvinyl alcohol/nano-cellulose mixed solution, and slightly stirring by using a mechanical stirrer. Adding a green reducing agent D-fructose, wherein the mass ratio of the reducing agent to the graphene oxide is 10:1, and adjusting the pH value of the solution to 9 by using ammonia water. And then placing the mixture in a water bath at 95 ℃ for reaction for 2h, and then carrying out ultrasonic treatment for 5min to obtain a polyvinyl alcohol/nano-cellulose/graphene mixed solution. And standing for 24 hours, pouring the mixture on a glass substrate, drying at room temperature, uncovering the film, and crushing into powder to obtain the polyvinyl alcohol/nano-cellulose/graphene composite material.
S20, preparation of high-stability oxygen-resistant pipe
Taking 100 parts of heat-resistant polyethylene, 1.5 parts of color master batch, 1 part of antioxidant (the antioxidant comprises a main antioxidant and an auxiliary antioxidant in a mass ratio of 1: 0.1, the main antioxidant is 2, 8-di-tert-butyl 4-methylphenol, the auxiliary antioxidant is pentaerythritol phosphite), 1.5 parts of PPA and 2.5 parts of polyvinyl alcohol/nano-cellulose/graphene polymer, uniformly mixing in a mixer to obtain a premix, wherein the premix is prepared by melting, blending and extruding by a double-screw extruder, the first-stage extrusion temperature is 190 ℃, the second-stage extrusion temperature is 200 ℃, the third-stage extrusion temperature is 195 ℃, the fourth-stage extrusion temperature is 200 ℃, the first-stage die head temperature is 200 ℃, the second-stage die head temperature is 220 ℃, the third-stage die head temperature is 230 ℃, the fourth-stage die head temperature is 220 ℃, the fifth-stage die head temperature is 200 ℃, the vacuum degree is 0.03MPa, and the torque current is 80A, screw speed 105 rpm; and cooling and cutting to obtain the high-stability oxygen-resistant pipe.
Comparative example 1
S21, taking 100 parts of heat-resistant polyethylene, 1.5 parts of color master batch, 1 part of antioxidant (the antioxidant comprises a main antioxidant and an auxiliary antioxidant in a mass ratio of 1: 0.1, the main antioxidant is 2, 8-di-tert-butyl 4-methylphenol, the auxiliary antioxidant is pentaerythritol phosphite), 1.5 parts of PPA and 2.5 parts, uniformly mixing in a mixer to obtain a premix, and the premix is prepared by melt blending extrusion of a double-screw extruder, wherein the first-stage extrusion temperature is 190 ℃, the second-stage extrusion temperature is 200 ℃, the third-stage extrusion temperature is 195 ℃, the fourth-stage extrusion temperature is 200 ℃, the first-stage die head temperature is 200 ℃, the second-stage die head temperature is 220 ℃, the third-stage die head temperature is 230 ℃, the fourth-stage die head temperature is 220 ℃, the fifth-stage die head temperature is 200 ℃, the vacuum degree is 0.03MPa, the torque current is 80A, and the screw rotation speed is; and cooling and cutting to obtain the common polyethylene pipe.
Comparative example No. two
S22, taking 100 parts of heat-resistant polyethylene, 1.5 parts of color master batch, 1 part of antioxidant (the antioxidant comprises a main antioxidant and an auxiliary antioxidant in a mass ratio of 1: 0.1, the main antioxidant is 2, 8-di-tert-butyl 4-methylphenol, the auxiliary antioxidant is pentaerythritol phosphite), 1.5 parts of PPA and 1 part of polyvinyl alcohol nanofiber, and uniformly mixing in a mixer to obtain a premix, wherein the premix is prepared by melt blending extrusion of a twin-screw extruder, the first-stage extrusion temperature is 190 ℃, the second-stage extrusion temperature is 200 ℃, the third-stage extrusion temperature is 195 ℃, the fourth-stage extrusion temperature is 200 ℃, the first-stage die head temperature is 200 ℃, the second-stage die head temperature is 220 ℃, the third-stage die head temperature is 230 ℃, the fourth-stage die head temperature is 220 ℃, the fifth-stage die head temperature is 200 ℃, the vacuum degree is 0.03MPa, the torque current is 80A, and the screw rotation speed is; and cooling and cutting to obtain the common polyethylene pipe.
Comparative example No. three
S23, taking 100 parts of heat-resistant polyethylene, 1.5 parts of color master batch, 1 part of antioxidant (the antioxidant comprises a main antioxidant and an auxiliary antioxidant in a mass ratio of 1: 0.1, the geosynthetic antioxidant is 2, 8-di-tert-butyl 4-methylphenol, the auxiliary antioxidant is pentaerythritol phosphite), 1.5 parts of PPA and 2.5 parts of polyvinyl alcohol nanofiber, uniformly mixing in a mixer to obtain a premix, and performing melt blending extrusion preparation on the premix by using a twin-screw extruder, wherein the first-stage extrusion temperature is 190 ℃, the second-stage extrusion temperature is 200 ℃, the third-stage extrusion temperature is 195 ℃, the fourth-stage extrusion temperature is 200 ℃, the first-stage die head temperature is 200 ℃, the second-stage die head temperature is 220 ℃, the third-stage die head temperature is 230 ℃, the fourth-stage die head temperature is 220 ℃, the fifth-stage die head temperature is 200 ℃, the vacuum degree is 0.03MPa, the torque current is 80A, and the screw; and cooling and cutting to obtain the common polyethylene pipe.
Comparative example No. four
S24, preparing a graphene oxide composite pipe, namely taking 100 parts of heat-resistant polyethylene, 1.5 parts of color master batch, 1 part of antioxidant (the antioxidant comprises a main antioxidant and an auxiliary antioxidant in a mass ratio of 1: 0.1, the main antioxidant is 2, 8-di-tert-butyl 4-methylphenol, the auxiliary antioxidant is pentaerythritol phosphite), 1.5 parts of PPA, and 2.5 parts of polyvinyl alcohol/nano-cellulose/graphene oxide polymer obtained without adding a reducing agent in the preparation process of the invention, uniformly mixing the mixture in a mixer to obtain a premix, melting, blending and extruding the premix by using a double-screw extruder, wherein the first-stage extrusion temperature is 190 ℃, the second-stage extrusion temperature is 200 ℃, the third-stage extrusion temperature is 195 ℃, the fourth-stage extrusion temperature is 200 ℃, the second-stage die temperature is 220 ℃, the third-stage die temperature is 230 ℃, the temperature of the fourth section of die head is 220 ℃, the temperature of the fifth section of die head is 200 ℃, the vacuum degree is 0.03MPa, the torque current is 80A, and the rotating speed of the screw is 105 rpm; and cooling and cutting to obtain the graphene oxide composite pipe.
The following experiments are adopted to verify the effect of the invention:
experiment one: pipe oxygen permeability coefficient analysis
The oxygen permeability test experiment is carried out according to ISO 17455-:
table 1:
table 1 is the pipe oxygen permeability coefficient data for the comparative examples and examples. It can be seen that the oxygen permeability of examples one to five is lower than that of comparative examples one to four, which indicates that the composite pipe prepared by using the polyvinyl alcohol/nanocellulose/graphene polymer has better oxygen barrier property. In addition, the oxygen permeability of the first to fifth examples is lower than that of the comparative example 4, which shows that the composite pipe prepared by using the reduced graphene oxide has lower oxygen permeability than that of the graphene oxide, and the pipe material prepared by using the reduced graphene oxide instead of the graphene oxide has better oxygen barrier performance. Particularly, the oxygen permeability coefficient of the comparative example is the highest, and the oxygen barrier property is the worst; example 2 has the lowest oxygen permeability coefficient and the best oxygen barrier properties.
Experiment two, oxidation induction experiment
OIT experiments were carried out according to GB/T19466.6-2009 part 6-oxidation induction time (isothermal OIT) for examples one to five and comparative example four, yielding the data in Table 2:
table 2:
table 2 shows that the pipes prepared by using reduced graphene oxide in the first to fifth examples have longer oxidation induction time than the pipes prepared by using graphene oxide, which indicates that the pipes prepared by using reduced graphene oxide have stronger stability than the graphene oxide material because the reduced graphene oxide completely removes the oxide group attached to the graphene oxide, so that the structure of the pipes is stable, and the prepared products are not deteriorated due to chemical reaction caused by excessive activity. In particular, the oxidation induction time is longest and the stability is the best in example 2.
Experiment III, testing stability of pipe
The hydrostatic test is carried out according to GB/T6111-2018 'determination of internal pressure resistance of thermoplastic plastic pipeline system for fluid transportation', and an A-shaped end socket is adopted. Hydrostatic pressure tests were performed on the tubing prepared in the above examples and comparative examples, respectively, and the following test data were obtained:
table 3:
table 3 is the pipe stability data for the comparative examples and examples. It can be seen that under the experimental conditions of 11.2MPa 20 ℃ 1h and 4.1MPa 95 ℃ 22h, all the pipes are not cracked and pass the detection. When the experimental condition is 4.0MPa 95 ℃ 165h, the comparative examples I to III are not qualified, and the comparative example IV is qualified in the test because the strength of the polymer added with the polyvinyl alcohol/the nano-cellulose/the graphene oxide is increased; in addition, the strength of the first to fifth examples is also enhanced due to the addition of the polyvinyl alcohol/nano-cellulose/graphene polymer, and the test is qualified. When the test conditions reach 3.8MPa and the temperature reaches 95 ℃, the pipe is broken in each proportion after 1000 hours, so that the pipe is unqualified, and the first to fifth embodiments still have good stability and pass the test. Because the polyvinyl alcohol/nano-cellulose/graphene polymer is added in the first to fifth embodiments, the strength of the pipe is enhanced. In particular, the reduced graphene oxide materials are used in the first to fifth examples, which are superior to the comparative example four in strength, which indicates that the use of the reduced graphene oxide is more advantageous to the stability of the pipe compared with the graphene oxide, because the reduced graphene oxide completely removes the oxide groups attached to the graphene oxide, so that the structure of the pipe is stabilized, and the pipe is prevented from being cracked due to static pressure test caused by deterioration of the prepared product due to chemical reaction caused by over-activity.
The invention is not limited to only that described in the specification and embodiments, and thus additional advantages and modifications will readily occur to those skilled in the art, and it is not intended to be limited to the specific details, representative apparatus, and examples shown and described herein, without departing from the spirit and scope of the general concept as defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of a high-stability oxygen-barrier pipe is characterized by comprising the following steps:
1) preparing a polyvinyl alcohol/nano cellulose composite material by a casting method;
2) preparation of polyvinyl alcohol/nanocellulose/graphene polymer: mixing the composite material solution obtained in the step 1) with a graphene oxide aqueous solution, adding a reducing agent, reacting in an alkaline environment, and pouring to obtain a polyvinyl alcohol/nano-cellulose/graphene composite material;
3) preparing an oxygen barrier pipe: mixing the polyvinyl alcohol/nano-cellulose/graphene polymer obtained in the step 2) with heat-resistant polyethylene, color master batch, antioxidant and polyphthalamide, and then co-extruding to obtain the oxygen-resistant pipe.
2. The method for preparing the high-stability oxygen-barrier tube material as claimed in claim 1, wherein the method comprises the following steps: the casting method in the step 1) comprises the following steps: dissolving polyvinyl alcohol particles in distilled water, stirring at 80-100 ℃ to obtain a polyvinyl alcohol solution, standing for defoaming, pouring the polyvinyl alcohol solution on a glass substrate, drying at room temperature, and grinding into powder; mixing the nano-cellulose suspension with polyvinyl alcohol, stirring, performing ultrasonic treatment, standing, pouring into a glass substrate, drying at room temperature, and grinding into powder to obtain the polyvinyl alcohol/nano-cellulose composite material.
3. The method for preparing the high-stability oxygen-barrier tube material as claimed in claim 1, wherein the method comprises the following steps: step 2) mixing 1-5 parts by weight of graphite oxide and 5 parts by weight of polyvinyl alcohol/nano-cellulose, dissolving, stirring, adding a green reducing agent, and adjusting the pH value to be alkaline by using ammonia water; then carrying out reaction in a water bath, and carrying out ultrasonic treatment to obtain a polyvinyl alcohol/nano-cellulose/graphene mixed solution; and standing, pouring the mixture on a glass substrate, drying, uncovering the film, and crushing the film into powder to obtain the polyvinyl alcohol/nano-cellulose/graphene composite material.
4. The method for preparing the high-stability oxygen-barrier pipe material according to claim 1, wherein the antioxidant in the step 3) is prepared by mixing the following components in a mass ratio of 1: 0.1 of 2, 8-di-tert-butyl 4-methylphenol and pentaerythritol phosphite, wherein the mass ratio of the polyvinyl alcohol/nano-cellulose/graphene polymer to the heat-resistant polyethylene, the color master batch, the antioxidant and the polyphthalamide is (1-2.5): 100:1.5:1:1.5.
5. The method for preparing the high-stability oxygen barrier pipe material according to claim 1 or 2, wherein the polyvinyl alcohol particles and the distilled water are stirred for 2 hours in the step 1); the mass fraction of the nano-cellulose suspension is 0.8%; the nano-cellulose accounts for 10% of the mass of the polyvinyl alcohol.
6. The method for preparing the high-stability oxygen barrier pipe material as claimed in claim 1 or 2, wherein: the mixing and stirring time in the step 1) is 1 hour, and the standing time is 24 hours.
7. The high-stability oxygen barrier tube material and the preparation method thereof according to claim 1 or 3, wherein the mass concentration of the graphene oxide aqueous solution in the step 2) is 0.5 mg/mL.
8. The high-stability oxygen barrier tube material and the preparation method thereof according to claim 1 or 3, wherein the reducing agent in the step 2) is D-fructose, and the mass ratio of the D-fructose to the graphene oxide is (10-5): 1.
9. the method for preparing a high stability oxygen barrier tube according to claim 1 or 3, wherein the pH value is adjusted to 8-9 by ammonia water in step 2); the water bath reaction is carried out at 95 ℃ for 2 hours; the ultrasonic treatment time is 5 min.
10. The method for preparing an oxygen barrier tube with high stability as claimed in claim 1 or 4, wherein the co-extrusion process in step 3) is as follows: the premix is prepared by melt blending extrusion of a twin-screw extruder, wherein the extrusion temperature of a first section is 190 ℃, the extrusion temperature of a second section is 200 ℃, the extrusion temperature of a third section is 195 ℃, the extrusion temperature of a fourth section is 200 ℃, the die head temperature of the first section is 200 ℃, the die head temperature of the second section is 220 ℃, the die head temperature of the third section is 230 ℃, the die head temperature of the fourth section is 220 ℃, the die head temperature of a fifth section is 200 ℃, the vacuum degree is 0.03MPa, the torque current is 80A, and the screw rotation speed is 105 rpm; and cooling and cutting to obtain the high-stability oxygen-resistant pipe.
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