CN111303519B - Corrosion-resistant heat-insulating building material surface composite film and preparation process thereof - Google Patents
Corrosion-resistant heat-insulating building material surface composite film and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a corrosion-resistant heat-insulating building material surface composite film which comprises a modified graphene film and a modified polyethylene heat-insulating film, wherein the modified graphene film is prepared from the following raw materials in parts by weight: 20-30 parts of graphene, 10-15 parts of sodium nitrate, 200-250 parts of 98% concentrated sulfuric acid, 2-4 parts of potassium chlorate, 50-70 parts of 10% hydrogen peroxide aqueous solution, 60-90 parts of dodecylamine and 8-15 parts of polyacrylamide; the invention also discloses a preparation process of the corrosion-resistant heat-preservation building material surface composite film; the modified graphene film not only has excellent corrosion resistance, but also reduces the surface energy of the modified graphene film, so that the composite capability of the modified graphene film and a matrix can be enhanced; the technical problem that the graphene film prepared by the method cannot be uniformly compounded with a matrix is solved, wherein super-strong van der Waals force and conjugate acting force exist between the graphene, a three-dimensional structure is easy to form, so that the dispersibility of the graphene film in an organic phase and an aqueous phase solvent is poor.
Description
Technical Field
The invention belongs to the technical field of composite films, and particularly relates to a corrosion-resistant heat-preservation building material surface composite film and a preparation process thereof.
Background
Due to environmental reasons, corrosion phenomena often occur in the production and later storage processes of the heat-insulating building materials, and the corrosion phenomena bring adverse effects to the mechanical properties of the heat-insulating building materials and the corrosion resistance in the use process, so that the service life of the heat-insulating building materials is seriously influenced.
The Chinese patent No. CN104788795A discloses a corrosion-resistant film material and a preparation method thereof, wherein the packaging material mainly comprises a carrier material, adhesive resin and phenol for high-temperature adhesiveAldehyde epoxy resin; the carrier material is prepared from the following raw materials in parts by weight: 2-13 parts of ethylene-vinyl acetate copolymer, 2-13 parts of high polymer polypropylene and 1-14 parts of polysulfone, wherein the quantitative requirement of the ethylene-vinyl acetate copolymer is 20-35g/m 2 High polymer polypropylene 15-25g/m 2 Polysulfone 13-30g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The binding resin is melamine formaldehyde resin or melamine urea formaldehyde resin suitable for impregnation, wherein the resin solid content is 41-52%. The corrosion-resistant film material prepared by the method has the characteristics of strong stretching capability, good weather resistance and moderate deformation temperature; and is resistant to strong acid, strong alkali and organic solvents; convenient use and simple operation.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a corrosion-resistant heat-insulating building material surface composite film and a preparation process thereof.
The invention aims to solve the technical problems that:
(1) The graphene film prepared by the method cannot be uniformly compounded with a matrix;
(2) The polyethylene molecular structure is compact, when the film prepared by the polyethylene molecular structure is adhered to other films through the adhesive, the adhesive molecules are not easy to enter the polyethylene molecules, so that the polyethylene film and other films are poor in integrity after being compounded, and the phenomena of layering, adhesive opening and the like are easy to occur.
The aim of the invention can be achieved by the following technical scheme:
the composite film comprises a modified graphene film and a modified polyethylene heat-insulating film, and is prepared by the following method:
firstly, preparing a modified polyethylene heat-insulating film:
s1, mixing deionized water and absolute ethyl alcohol according to the weight ratio of 10:1, heating in a water bath at 45 ℃, adding a coupling agent, magnetically stirring for 30min to obtain a mixed solution, ball-milling chitosan, controlling the ball-milling rotation speed to 300r/min, ball-milling for 2h, adding the mixed solution, stirring for 2h at the rotation speed of 120r/min, carrying out suction filtration, washing for 3 times with absolute ethyl alcohol, transferring to a vacuum drying oven at 80 ℃ for drying for 5h, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, and obtaining primarily treated chitosan particles, wherein the weight ratio of chitosan to the mixed solution is controlled to be 1:10-13;
s2, mixing the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment, drying at 110 ℃ for 4 hours, heating to 150-205 ℃, reacting for 2 hours at the temperature to obtain a mixed melt, casting to form a film, and preparing a heat preservation film, wherein the weight ratio of the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment is controlled to be 0.8-1.0:95-98:8-10:8-10;
and secondly, compounding the modified polyethylene heat-insulating film and the modified graphene film through an adhesive to prepare the corrosion-resistant heat-insulating building material surface composite film.
In the step S1, the ball-milled chitosan is subjected to preliminary treatment by a coupling agent, in the step S2, chitosan particles, polyethylene particles, aminopropyl methyl diethoxy silane and pentaerythritol diphosphite are mixed and cast into a film, polar groups can be added on a polyethylene molecular chain by the chitosan in the film forming process, so that the crystallinity is reduced, the molecular structure is not compact, the chitosan is a hydrophilic substance, and a large number of hydrophilic groups exist on the surface, so that the polyethylene molecular structure modified by the chitosan is not compact, when the thermal insulation film prepared by the chitosan is adhered to the modified graphene film by an adhesive, the adhesive molecules are easier to enter the polyethylene molecules, the integrity of the thermal insulation film and the modified graphene film is enhanced, the phenomena of layering, glue opening and the like are prevented, and the film cast by the chitosan and the polyethylene has excellent thermal insulation performance, so that the finally prepared composite film has good thermal insulation performance.
Further, the modified graphene film is prepared from the following raw materials in parts by weight: 20-30 parts of graphene, 10-15 parts of sodium nitrate, 200-250 parts of 98% concentrated sulfuric acid by volume fraction, 2-4 parts of potassium chlorate, 50-70 parts of 10% hydrogen peroxide aqueous solution by mass fraction, 60-90 parts of dodecylamine and 8-15 parts of polyacrylamide.
Further, the modified graphene film is prepared by the following method:
(1) Adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, adding potassium chlorate, continuously stirring for 30min, heating in a water bath at 40 ℃ for reaction for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, and adding 10% hydrogen peroxide aqueous solution for continuous reaction for 10min to obtain graphene oxide solution;
(2) Adding dodecylamine into absolute ethyl alcohol, magnetically stirring for 15min, adding the graphene oxide solution prepared in the step (1), carrying out ultrasonic treatment for 30min, magnetically stirring for 12h, filtering, washing, transferring to a drying oven at 80 ℃ and drying for 4h to prepare modified graphene oxide;
(3) Dispersing the dried modified graphene oxide in a xylene solution, heating to 110 ℃, adding polyacrylamide, magnetically stirring for 30min, cooling to 75 ℃, continuously stirring until drying, and then pressing the film at 150 ℃ to obtain the modified graphene film.
The graphene has super-strong van der Waals force and conjugation acting force, a three-dimensional structure is easy to form, so that the graphene has poor dispersibility in organic phase and aqueous phase solvents, in the step (1), the graphene is prepared into graphene oxide under the actions of potassium chlorate, 10% hydrogen peroxide aqueous solution and the like, the graphene oxide can be dispersed in water and also can be dispersed in the organic solvents, and abundant oxygen-containing functional groups are added on the surface of the graphene oxide, so that agglomeration is difficult to occur; and (2) modifying graphene oxide, controlling the weight ratio of the graphene oxide to dodecylamine to be 1:3, enabling carboxyl on the graphene oxide to react with dodecylamine amino, enabling carboxyl to be replaced by amino, and controlling the weight ratio to be 1:3, enabling carboxyl to be completely replaced by amino, so as to obtain modified graphene oxide, wherein the modified graphene oxide is changed from hydrophilicity to hydrophobicity, further, in the step (3), the modified graphene oxide can be dispersed in xylene, further, a uniform modified graphene film can be prepared, the modified graphene film not only has excellent corrosion resistance, but also has reduced surface energy, and further, the composite capability of the modified graphene film and a matrix can be enhanced.
Further, in the first step S1, the coupling agent is one or both of KH550 and KH 560.
Further, the adhesive in the second step is one or two of water-based plastic composite adhesive and pressure-sensitive adhesive.
A preparation process of a corrosion-resistant heat-insulating building material surface composite film comprises the following steps:
firstly, preparing a modified polyethylene heat-insulating film:
s1, mixing deionized water and absolute ethyl alcohol according to the weight ratio of 10:1, heating in a water bath at 45 ℃, adding a coupling agent, magnetically stirring for 30min to obtain a mixed solution, ball-milling chitosan, controlling the ball-milling rotation speed to 300r/min, ball-milling for 2h, adding the mixed solution, stirring for 2h at the rotation speed of 120r/min, carrying out suction filtration, washing for 3 times with absolute ethyl alcohol, transferring to a vacuum drying oven at 80 ℃ for drying for 5h, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, and obtaining primarily treated chitosan particles, wherein the weight ratio of chitosan to the mixed solution is controlled to be 1:10-13;
s2, mixing the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment, drying at 110 ℃ for 4 hours, heating to 150-205 ℃, reacting for 2 hours at the temperature to obtain a mixed melt, casting to form a film, and preparing a heat preservation film, wherein the weight ratio of the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment is controlled to be 0.8-1.0:95-98:8-10:8-10;
and secondly, compounding the modified polyethylene heat-insulating film and the modified graphene film through an adhesive to prepare the corrosion-resistant heat-insulating building material surface composite film.
The invention has the beneficial effects that:
(1) The invention relates to a corrosion-resistant heat-insulating building material surface composite film which comprises a modified graphene film and a modified polyethylene heat-insulating film, wherein in the preparation process of the modified polyethylene heat-insulating film, the ball-milled chitosan is subjected to preliminary treatment by a coupling agent in the step S1, chitosan particles, polyethylene particles, aminopropyl methyl diethoxy silane and pentaerythritol diphosphite are mixed and cast to form a film in the step S2, polar groups can be added on a polyethylene molecular chain by the chitosan in the film forming process, so that the crystallinity is reduced, the molecular structure is not compact, the chitosan is a hydrophilic substance, and a large number of hydrophilic groups exist on the surface, so that the polyethylene molecular structure modified by the chitosan is not compact, when the heat-insulating film prepared by the chitosan is adhered to the modified graphene film by an adhesive, the adhesive molecules are easier to enter the polyethylene molecules, the integrity of the heat-insulating film and the modified graphene film is enhanced, the phenomena of layering, glue opening and the like are prevented, and the film formed by casting by the chitosan and the polyethylene has excellent heat-insulating performance, and the excellent heat-insulating performance is endowed to the finally prepared composite film; the technical problems that the polyethylene film has a compact structure, when the film prepared by the polyethylene film is adhered to other films by an adhesive, the adhesive molecules are not easy to enter the polyethylene molecules, the polyethylene film and the other films are poor in integrity after being compounded, and layering, adhesive opening and the like are easy to occur are solved;
(2) In the preparation process of the modified graphene film, graphene is prepared into graphene oxide under the actions of potassium chlorate, 10% hydrogen peroxide aqueous solution and the like in the step (1), the graphene oxide can be dispersed in water or an organic solvent, and rich oxygen-containing functional groups are added on the surface of the graphene oxide, so that agglomeration is not easy to occur; the graphene oxide is modified in the step (2), the weight ratio of the graphene oxide to the dodecylamine is controlled to be 1:3, carboxyl on the graphene oxide is reacted with the dodecylamine amino, the carboxyl is replaced by the amino, the carboxyl is completely replaced by the amino when the weight ratio is controlled to be 1:3, and modified graphene oxide is prepared, the modified graphene oxide is changed from hydrophilicity to hydrophobicity, and further, the modified graphene oxide can be dispersed in dimethylbenzene in the step (3), so that a uniform modified graphene film can be prepared, the modified graphene film not only has excellent corrosion resistance, but also has reduced surface energy, and further, the composite capability of the modified graphene film and a matrix can be enhanced; the technical problem that the graphene film prepared by the method cannot be uniformly compounded with a matrix is solved, wherein super-strong van der Waals force and conjugate acting force exist between the graphene, a three-dimensional structure is easy to form, so that the dispersibility of the graphene film in an organic phase and an aqueous phase solvent is poor.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The composite film comprises a modified graphene film and a modified polyethylene heat-insulating film, and is prepared by the following method:
firstly, preparing a modified polyethylene heat-insulating film:
step S1, mixing deionized water and absolute ethyl alcohol according to the weight ratio of 10:1, heating in a 45 ℃ water bath, adding KH550, magnetically stirring for 30min to obtain mixed liquor, ball-milling chitosan, controlling the ball-milling rotation speed to 300r/min, ball-milling for 2h, adding the mixed liquor, stirring for 2h at the rotation speed of 120r/min, carrying out suction filtration, washing with absolute ethyl alcohol for 3 times, transferring to a 80 ℃ vacuum drying oven, drying for 5h, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, and obtaining primarily treated chitosan particles, wherein the weight ratio of chitosan to the mixed liquor is controlled to be 1:10;
s2, mixing the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment, drying at 110 ℃ for 4 hours, heating to 180 ℃, reacting for 2 hours at the temperature to obtain a mixed melt, casting to form a film, and preparing a heat-insulating film, wherein the weight ratio of the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment is controlled to be 0.8:95:8:8;
and secondly, compounding the modified polyethylene heat-insulating film and the modified graphene film through a pressure-sensitive adhesive to prepare the corrosion-resistant heat-insulating building material surface composite film.
The modified graphene film is prepared from the following raw materials in parts by weight: 20 parts of graphene, 10 parts of sodium nitrate, 200 parts of 98% concentrated sulfuric acid, 2 parts of potassium chlorate, 50 parts of 10% hydrogen peroxide aqueous solution, 60 parts of dodecylamine and 8 parts of polyacrylamide.
The modified graphene film is prepared by the following method:
(1) Adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, adding potassium chlorate, continuously stirring for 30min, heating in a water bath at 40 ℃ for reaction for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, and adding 10% hydrogen peroxide aqueous solution for continuous reaction for 10min to obtain graphene oxide solution;
(2) Adding dodecylamine into absolute ethyl alcohol, magnetically stirring for 15min, adding the graphene oxide solution prepared in the step (1), carrying out ultrasonic treatment for 30min, magnetically stirring for 12h, filtering, washing, transferring to a drying oven at 80 ℃ and drying for 4h to prepare modified graphene oxide;
(3) Dispersing the dried modified graphene oxide in a xylene solution, heating to 110 ℃, adding polyacrylamide, magnetically stirring for 30min, cooling to 75 ℃, continuously stirring until drying, and then pressing the film at 150 ℃ to obtain the modified graphene film.
Example 2
The composite film comprises a modified graphene film and a modified polyethylene heat-insulating film, and is prepared by the following method:
firstly, preparing a modified polyethylene heat-insulating film:
step S1, mixing deionized water and absolute ethyl alcohol according to the weight ratio of 10:1, heating in a 45 ℃ water bath, adding KH550, magnetically stirring for 30min to obtain mixed liquor, ball-milling chitosan, controlling the ball-milling rotation speed to 300r/min, ball-milling for 2h, adding the mixed liquor, stirring for 2h at the rotation speed of 120r/min, carrying out suction filtration, washing with absolute ethyl alcohol for 3 times, transferring to a 80 ℃ vacuum drying oven, drying for 5h, controlling the vacuum degree of the vacuum drying oven to-0.10 MPa, and obtaining primarily treated chitosan particles, wherein the weight ratio of chitosan to the mixed liquor is controlled to be 1:12;
s2, mixing the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment, drying at 110 ℃ for 4 hours, heating to 180 ℃, reacting for 2 hours at the temperature to obtain a mixed melt, casting to form a film, and preparing a heat-insulating film, wherein the weight ratio of the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment is controlled to be 0.8:96:8:9;
and secondly, compounding the modified polyethylene heat-insulating film and the modified graphene film through a pressure-sensitive adhesive to prepare the corrosion-resistant heat-insulating building material surface composite film.
The procedure is as in example 1.
Example 3
The composite film comprises a modified graphene film and a modified polyethylene heat-insulating film, and is prepared by the following method:
firstly, preparing a modified polyethylene heat-insulating film:
step S1, mixing deionized water and absolute ethyl alcohol according to the weight ratio of 10:1, heating in a 45 ℃ water bath, adding KH550, magnetically stirring for 30min to obtain mixed liquor, ball-milling chitosan, controlling the ball-milling rotation speed to 300r/min, ball-milling for 2h, adding the mixed liquor, stirring for 2h at the rotation speed of 120r/min, carrying out suction filtration, washing with absolute ethyl alcohol for 3 times, transferring to a 80 ℃ vacuum drying oven, drying for 5h, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, and obtaining primarily treated chitosan particles, wherein the weight ratio of chitosan to the mixed liquor is controlled to be 1:13;
s2, mixing the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment, drying at 110 ℃ for 4 hours, heating to 180 ℃, reacting for 2 hours at the temperature to obtain a mixed melt, casting to form a film, and preparing a heat-insulating film, wherein the weight ratio of the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment is controlled to be 1.0:98:8:10;
and secondly, compounding the modified polyethylene heat-insulating film and the modified graphene film through a pressure-sensitive adhesive to prepare the corrosion-resistant heat-insulating building material surface composite film.
The procedure is as in example 1.
Example 4
The composite film comprises a modified graphene film and a modified polyethylene heat-insulating film, and is prepared by the following method:
firstly, preparing a modified polyethylene heat-insulating film:
step S1, mixing deionized water and absolute ethyl alcohol according to the weight ratio of 10:1, heating in a 45 ℃ water bath, adding KH550, magnetically stirring for 30min to obtain mixed liquor, ball-milling chitosan, controlling the ball-milling rotation speed to 300r/min, ball-milling for 2h, adding the mixed liquor, stirring for 2h at the rotation speed of 120r/min, carrying out suction filtration, washing with absolute ethyl alcohol for 3 times, transferring to a 80 ℃ vacuum drying oven, drying for 5h, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, and obtaining primarily treated chitosan particles, wherein the weight ratio of chitosan to the mixed liquor is controlled to be 1:13;
s2, mixing the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment, drying at 110 ℃ for 4 hours, heating to 180 ℃, reacting for 2 hours at the temperature to obtain a mixed melt, casting to form a film, and preparing a heat-insulating film, wherein the weight ratio of the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment is controlled to be 1.0:98:10:10;
and secondly, compounding the modified polyethylene heat-insulating film and the modified graphene film through a pressure-sensitive adhesive to prepare the corrosion-resistant heat-insulating building material surface composite film.
The procedure is as in example 1.
Comparative example 1
In this comparative example, a polyethylene film was used instead of the modified polyethylene heat-insulating film as compared with example 1, and the preparation method was as follows:
firstly, mixing polyethylene particles, aminopropyl methyl diethoxy silane and pentaerythritol diphosphite, drying at 110 ℃ for 4 hours, then heating to 180 ℃, reacting at the temperature for 2 hours to obtain a mixed melt, casting to form a film, and obtaining a heat-insulating film, wherein the weight ratio of the polyethylene particles to the aminopropyl methyl diethoxy silane to the pentaerythritol diphosphite is controlled to be 95:8:8;
and secondly, compounding the polyethylene film and the modified graphene film through a pressure-sensitive adhesive to prepare the corrosion-resistant heat-preservation building material surface composite film.
Comparative example 2
In this comparative example, compared with example 1, the graphene film was used instead of the modified graphene film, and the preparation method is as follows:
firstly, preparing a modified polyethylene heat-insulating film:
step S1, mixing deionized water and absolute ethyl alcohol according to the weight ratio of 10:1, heating in a 45 ℃ water bath, adding KH550, magnetically stirring for 30min to obtain mixed liquor, ball-milling chitosan, controlling the ball-milling rotation speed to 300r/min, ball-milling for 2h, adding the mixed liquor, stirring for 2h at the rotation speed of 120r/min, carrying out suction filtration, washing with absolute ethyl alcohol for 3 times, transferring to a 80 ℃ vacuum drying oven, drying for 5h, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, and obtaining primarily treated chitosan particles, wherein the weight ratio of chitosan to the mixed liquor is controlled to be 1:10;
s2, mixing the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment, drying at 110 ℃ for 4 hours, heating to 180 ℃, reacting for 2 hours at the temperature to obtain a mixed melt, casting to form a film, and preparing a heat-insulating film, wherein the weight ratio of the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment is controlled to be 0.8:95:8:8;
and secondly, compounding the modified polyethylene heat-insulating film and the graphene film through a pressure-sensitive adhesive to prepare the corrosion-resistant heat-insulating building material surface composite film.
Comparative example 3
The comparative example is a composite film on the surface of a heat-insulating building material in the market.
The corrosion resistance, heat retaining property and tensile strength of examples 1 to 4 and comparative examples 1 to 3 were tested, and the results are shown in the following table;
as shown in the table above, examples 1 to 4 have a pH resistance in the range of 3.2 to 11.0, a good heat insulation performance, a tensile strength of 54 to 58MPa, comparative examples 1 to 3 have a pH resistance in the range of 4.0 to 11.0, comparative example 1 has a heat insulation performance generally good, and comparative examples 2 to 3 have a tensile strength of 42 to 45MPa. The modified graphene film not only has excellent corrosion resistance, but also reduces the surface energy of the modified graphene film, so that the composite capacity of the modified graphene film and a matrix can be enhanced; the technical problem that the graphene film prepared by the method cannot be uniformly compounded with a matrix is solved, wherein super-strong van der Waals force and conjugate acting force exist between the graphene, a three-dimensional structure is easy to form, so that the dispersibility of the graphene film in an organic phase and an aqueous phase solvent is poor.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (4)
1. The corrosion-resistant heat-insulating building material surface composite film is characterized by comprising a modified graphene film and a modified polyethylene heat-insulating film, and is prepared by the following method:
firstly, preparing a modified polyethylene heat-insulating film:
s1, mixing deionized water and absolute ethyl alcohol according to the weight ratio of 10:1, heating in a water bath at 45 ℃, adding a coupling agent, magnetically stirring for 30min to obtain a mixed solution, ball-milling chitosan, controlling the ball-milling rotation speed to 300r/min, ball-milling for 2h, adding the mixed solution, stirring for 2h at the rotation speed of 120r/min, carrying out suction filtration, washing for 3 times with absolute ethyl alcohol, transferring to a vacuum drying oven at 80 ℃ for drying for 5h, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, and obtaining primarily treated chitosan particles, wherein the weight ratio of chitosan to the mixed solution is controlled to be 1:10-13;
s2, mixing the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment, drying at 110 ℃ for 4 hours, heating to 150-205 ℃, reacting for 2 hours at the temperature to obtain a mixed melt, casting to form a film, and preparing a heat preservation film, wherein the weight ratio of the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment is controlled to be 0.8-1.0:95-98:8-10:8-10;
the second step, compounding the modified polyethylene heat-insulating film and the modified graphene film through an adhesive to prepare the corrosion-resistant heat-insulating building material surface composite film;
the modified graphene film is prepared from the following raw materials in parts by weight: 20-30 parts of graphene, 10-15 parts of sodium nitrate, 200-250 parts of 98% concentrated sulfuric acid, 2-4 parts of potassium chlorate, 50-70 parts of 10% hydrogen peroxide aqueous solution, 60-90 parts of dodecylamine and 8-15 parts of polyacrylamide;
the modified graphene film is prepared by the following method:
(1) Adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, adding potassium chlorate, continuously stirring for 30min, heating in a water bath at 40 ℃ for reaction for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, and adding 10% hydrogen peroxide aqueous solution for continuous reaction for 10min to obtain graphene oxide solution;
(2) Adding dodecylamine into absolute ethyl alcohol, magnetically stirring for 15min, adding the graphene oxide solution prepared in the step (1), carrying out ultrasonic treatment for 30min, magnetically stirring for 12h, filtering, washing, transferring to a drying oven at 80 ℃ and drying for 4h to prepare modified graphene oxide;
(3) Dispersing the dried modified graphene oxide in a xylene solution, heating to 110 ℃, adding polyacrylamide, magnetically stirring for 30min, cooling to 75 ℃, continuously stirring until drying, and then pressing the film at 150 ℃ to obtain the modified graphene film.
2. The corrosion-resistant heat-insulating building material surface composite film according to claim 1, wherein the coupling agent in the first step S1 is one or both of KH550 and KH 560.
3. The corrosion-resistant heat-insulating building material surface composite film according to claim 1, wherein the adhesive in the second step is one or two of an aqueous plastic composite adhesive and a pressure-sensitive adhesive.
4. The preparation process of the corrosion-resistant heat-insulating building material surface composite film is characterized by comprising the following steps of:
firstly, preparing a modified polyethylene heat-insulating film:
s1, mixing deionized water and absolute ethyl alcohol according to the weight ratio of 10:1, heating in a water bath at 45 ℃, adding a coupling agent, magnetically stirring for 30min to obtain a mixed solution, ball-milling chitosan, controlling the ball-milling rotation speed to 300r/min, ball-milling for 2h, adding the mixed solution, stirring for 2h at the rotation speed of 120r/min, carrying out suction filtration, washing for 3 times with absolute ethyl alcohol, transferring to a vacuum drying oven at 80 ℃ for drying for 5h, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, and obtaining primarily treated chitosan particles, wherein the weight ratio of chitosan to the mixed solution is controlled to be 1:10-13;
s2, mixing the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment, drying at 110 ℃ for 4 hours, heating to 150-205 ℃, reacting for 2 hours at the temperature to obtain a mixed melt, casting to form a film, and preparing a heat preservation film, wherein the weight ratio of the chitosan particles, the polyethylene particles, the aminopropyl methyl diethoxy silane and the pentaerythritol diphosphite after preliminary treatment is controlled to be 0.8-1.0:95-98:8-10:8-10;
the second step, compounding the modified polyethylene heat-insulating film and the modified graphene film through an adhesive to prepare the corrosion-resistant heat-insulating building material surface composite film;
the modified graphene film is prepared from the following raw materials in parts by weight: 20-30 parts of graphene, 10-15 parts of sodium nitrate, 200-250 parts of 98% concentrated sulfuric acid, 2-4 parts of potassium chlorate, 50-70 parts of 10% hydrogen peroxide aqueous solution, 60-90 parts of dodecylamine and 8-15 parts of polyacrylamide;
the modified graphene film is prepared by the following method:
(1) Adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, adding potassium chlorate, continuously stirring for 30min, heating in a water bath at 40 ℃ for reaction for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, and adding 10% hydrogen peroxide aqueous solution for continuous reaction for 10min to obtain graphene oxide solution;
(2) Adding dodecylamine into absolute ethyl alcohol, magnetically stirring for 15min, adding the graphene oxide solution prepared in the step (1), carrying out ultrasonic treatment for 30min, magnetically stirring for 12h, filtering, washing, transferring to a drying oven at 80 ℃ and drying for 4h to prepare modified graphene oxide;
(3) Dispersing the dried modified graphene oxide in a xylene solution, heating to 110 ℃, adding polyacrylamide, magnetically stirring for 30min, cooling to 75 ℃, continuously stirring until drying, and then pressing the film at 150 ℃ to obtain the modified graphene film.
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