CN109880353B - White graphene composite polyamide material, film and preparation method thereof - Google Patents
White graphene composite polyamide material, film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a white graphene composite polyamide material which comprises the following components in parts by weight: 0.5-20 parts of modified white graphene, 60-99.4 parts of polyamide resin and 0.1-20 parts of compatilizer. The invention also discloses a preparation method of the white graphene composite polyamide material, a polyamide film containing the white graphene composite polyamide material and a preparation method of the polyamide film. The white graphene composite polyamide film obtained by effectively and cooperatively utilizing the high strength, high barrier property and single-layer and few-layer transparent characteristics of the white graphene material and adopting the compatibility, uniform dispersion process, chemical covalent bonding effect and biaxial stretching process has high strength, high barrier property to oxygen and water vapor and a transparent structure, can effectively replace EVOH, MXD6 and aluminum foil barrier layer of the existing multilayer composite co-extrusion film, reduces the number of layers of the composite film, simplifies equipment investment and optimization process, reduces cost when the performance meets the requirements, and has wide market prospect.
Description
Technical Field
The invention relates to a polyamide material, and in particular relates to a white graphene composite polyamide material, a white graphene composite polyamide film and a preparation method of the white graphene composite polyamide film.
Background
The functional film packaging material is a plastic packaging material which is disputed to be developed and applied in countries around the world. Among them, the film having high barrier property is the most widely used and most important type of functional film material. The barrier film is particularly suitable for the packaging of meat food cold fresh packages and ham sausages, grains, medicines and health care products, generally has good barrier property, can block the quality change of oxygen and water vapor to the foods, effectively prolongs the quality guarantee period and shelf life of the foods, and has good use effect in the field of food and medicine packaging.
The barrier film is a multilayer co-extrusion composite film which is most representative and widely applied at present and is formed by melting, co-extruding and compounding different resin matrixes through a plurality of extruders, and the barrier film is mostly of a 3-layer structure and a 5-layer structure and even has a 9-layer and 11-layer composite structure. Most of barrier layers in the multilayer coextruded composite film are EVOH layers, MXD6 (modified polyamide) or aluminum foil layers, and the barrier layers are most popular barrier layer forms in the market. There are certain drawbacks in the barrier packaging industry. For example, in a multilayer composite film using EVOH or MXD6 as a barrier layer, EVOH and MXD6 have very strong barrier properties against oxygen, but have poorer barrier properties against water vapor as humidity in the environment increases; the multilayer composite film with the aluminium foil as the barrier layer is very high to steam, oxygen barrier nature, but the aluminium foil forms the crease easily after buckling many times, just worsens to oxygen, steam barrier nature, and the aluminium foil is opaque simultaneously, causes the consumer can't see the true commodity situation in the packing clearly, influences the purchase desire. Therefore, the composite film has a higher strength, a higher barrier property against oxygen and water vapor, and a higher transparency.
Disclosure of Invention
The invention aims to overcome the defects that the multi-layer co-extrusion composite film taking EVOH, MXD6 and aluminum foil as barrier layers on the market at present has poor oxygen and water vapor barrier properties and is opaque, and the process is complex and the cost is too high due to too large equipment investment, and provides a white graphene composite polyamide material, a white graphene composite polyamide film and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the white graphene composite polyamide material comprises the following components in parts by weight: 0.5-20 parts of modified white graphene, 60-99.4 parts of polyamide resin and 0.1-20 parts of compatilizer.
The white graphene composite polyamide material provided by the invention creatively uses white graphene as a few-layered two-dimensional material, and a film prepared from the polyamide material has high mechanical strength, flexibility, white or transparent property, and the like, and has the characteristics of high barrier property to water vapor, oxygen, carbon dioxide and the like. When the addition amount of the modified white graphene is more than 20 parts, agglomeration is easy to occur, and the cost is high.
As a preferred embodiment of the white graphene composite polyamide material of the present invention, the preparation method of the modified white graphene comprises the following steps:
(1) activating the white graphene under strong acid to obtain white graphene A;
(2) putting the white graphene A into an ethanol water solution, adding gamma-mercaptopropyl trimethoxysilane, stirring for reaction, taking out, and washing to obtain white graphene B;
(3) and adding the white graphene B into a solvent in which an acrylamide monomer is dissolved, adding a photoinitiator, irradiating by ultraviolet light, taking out, washing and drying to obtain the modified white graphene.
In the step (1), the purpose of the activation treatment is to generate active groups such as hydroxyl, carboxyl and the like on the surface of the white graphene; the conditions of the activation treatment were: carrying out reflux treatment on the white graphene for 0.5-12 h at 60-250 ℃ by using strong acid.
In the step (2), gamma-mercaptopropyl trimethoxysilane is adopted to carry out surface modification on the white graphene, the purpose of washing is to remove the gamma-mercaptopropyl trimethoxysilane remained on the surface of the white graphene, and the stirring reaction time is 0.5-6 h.
In the step (3), the time of ultraviolet irradiation is 0.1-6 h; washing to remove residual acrylamide monomer on the surface of the white graphene, wherein the drying temperature is 30-120 ℃.
According to the modified white graphene, a novel mercapto-alkene click addition reaction is used for mildly, quickly, controllably and effectively grafting acrylamide high polymer on the surface of the white graphene, so that good compatibility with a polypropylene matrix is really realized, the modified white graphene can achieve good uniform dispersion in the polyamide matrix and can also generate covalent chemical bonding with the polyamide matrix, and the generated bonding force is far greater than that of physical treatments such as simple filling, coating and adsorption of other manufacturers on the market.
As a preferred embodiment of the white graphene composite polyamide material, the white graphene, gamma-mercaptopropyltrimethoxysilane, an acrylamide monomer and a photoinitiator are prepared from the following components in parts by weight: 1 part of white graphene, 0.5-15 parts of gamma-mercaptopropyl trimethoxy silane, 10-50 parts of acrylamide monomer and 0.5-10 parts of photoinitiator. The preparation of the modified white graphene can be realized by adopting the above ratio.
As a more preferable embodiment of the white graphene composite polyamide material of the present invention, the white graphene, γ -mercaptopropyltrimethoxysilane, an acrylamide monomer and a photoinitiator are in parts by weight: 1 part of white graphene, 1-10 parts of gamma-mercaptopropyl-trimethoxysilane, 20-40 parts of acrylamide monomer and 0.5-5 parts of photoinitiator. By adopting the raw material proportion, the prepared modified white graphene has better performance.
In a preferred embodiment of the white graphene composite polyamide material, the modified white graphene is added in an amount of 1-15 parts by weight; the modified white graphene is 2-20 layers of modified white graphene.
When the modified white graphene is added in the above amount, the modified white graphene can fully play a role in a polyamide material, is easy to disperse, has no agglomeration phenomenon, and can ensure the performance of a polyamide film while controlling the production cost to be lower.
In a preferred embodiment of the white graphene composite polyamide material, the polyamide resin is 80 to 98.9 parts by weight, and the compatibilizer is 0.1 to 5 parts by weight.
When the proportion is adopted, the film prepared from the polyamide material has higher mechanical strength, flexibility, white or transparent property and higher barrier property to water vapor, oxygen, carbon dioxide and the like.
As a preferred embodiment of the white graphene composite polyamide material according to the present invention, at least one of the following (a) to (d):
(a) the strong acid species is nitric acid and/or sulfuric acid;
(b) in the step (3), the solvent used for dissolving the acrylamide monomer is at least one of deionized water, ethanol, propanol, isopropanol and butanol;
(c) the photoinitiator species is at least one of 250, 369, 184, 907, 500 and 1173 photoinitiators;
(d) the solvent adopted for washing is at least one of toluene, xylene, acetone, butanone and tetrahydrofuran.
As a preferred embodiment of the white graphene composite polyamide material, the polyamide resin is at least one of PA6, MXD6, PA66, PA10, PA11, PA12, PA46, PA610, PA1010 and PA 612; the compatilizer is PP grafted maleic anhydride. The polyamide resin may be at least one of PA6 (nylon 6), MXD6 (modified nylon 6), PA66 (nylon 66), PA10 (nylon 10), PA11 (nylon 11), PA12 (nylon 12), PA46 (nylon 46), PA610 (nylon 610), PA1010 (nylon 1010), and PA612 (nylon 612).
The invention also aims to provide a preparation method of the white graphene composite polyamide material, which comprises the following steps:
(A) starting a high-speed mixer, heating to 60-120 ℃, weighing polyamide resin, modified white graphene and a compatilizer, and premixing and dispersing for 5-30 min by a high-speed disperser;
(B) and (3) starting the double-screw extruder, keeping the temperature of each zone at 210-280 ℃, adding the premixed and dispersed material obtained in the step (A) into a charging barrel of the double-screw extruder after the material is stabilized, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite polyamide material.
The invention also aims to provide a polyamide film which comprises the white graphene composite polyamide material.
As a preferred embodiment of the polyamide film of the present invention, the polyamide film comprises the following components in parts by weight: 1-30 parts of the white graphene composite polyamide material and 70-99 parts of polyamide resin.
As a preferred embodiment of the polyamide film of the present invention, the polyamide film comprises the following components in parts by weight: 1-10 parts of the white graphene composite polyamide material and 90-99 parts of polyamide resin.
The invention also aims to provide a preparation method of the polyamide film, which comprises the following steps: starting a film casting machine, wherein the temperature of each zone is 210-280 ℃, after the stability, adding the white graphene composite polyamide material and the polyamide resin into a material cylinder of the film casting machine, and obtaining the polyamide film through extrusion, air cooling, longitudinal and transverse bidirectional stretching, heat setting and rolling; the longitudinal stretching ratio is 250-400%, and the longitudinal stretching heat setting temperature is 60-120 ℃; the transverse stretching ratio is 300-450%, and the transverse stretching heat setting temperature is 120-180 ℃. The modified white graphene and the polyamide matrix have good physicochemical binding effect, and the longitudinal and transverse biaxial stretching process is adopted, so that the lamellar white graphene can be uniformly and orderly arranged and spread in the polyamide matrix in an oriented manner, and the effect of high barrier property to oxygen and water vapor can be achieved by combining the excellent barrier property of the polyamide matrix.
The invention has the beneficial effects that: the invention provides a white graphene composite polyamide material, a film and a preparation method thereof, wherein the white graphene composite polyamide film obtained by effectively and synergistically matching the high strength, high barrier property and single and few-layer transparent characteristics of a white graphene material by adopting a compatibility, uniform dispersion process, chemical covalent bonding effect and biaxial stretching process has a transparent structure while having high strength and high barrier property to oxygen and water vapor, can effectively replace EVOH, MXD6 and an aluminum foil barrier layer of the existing multilayer composite co-extrusion film, reduces the number of layers of the composite film, simplifies equipment investment and optimization process, reduces cost while meeting the requirements of performance, and has wide market prospect. .
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
In an embodiment of the white graphene composite polyamide material according to the present invention, a formula of the white graphene composite polyamide material according to the embodiment is shown in table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1 part by weight of 2-20 layers of white graphene is subjected to reflux treatment for 2 hours at a high temperature of 100 ℃ by using mixed acid of nitric acid and sulfuric acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the white graphene; then placing the mixture into an ethanol water solution, adding 6 parts by weight of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 3.5 hours at normal temperature, and washing unreacted KH590 on the surface of the white graphene for multiple times by using acetone; and finally, placing the white graphene with the chemically modified KH590 on the surface into deionized water in which 30 parts by weight of acrylamide is dissolved in advance, adding 1.5 parts by weight of photoinitiator 1173, irradiating for 0.5h by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted acrylamide monomers on the surface of the white graphene for multiple times by using ethanol, and drying at 75 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite polyamide material comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 80 ℃, weighing MXD6, modified white graphene and PP grafted maleic anhydride (PP-g-MAH) in parts by weight, premixing and dispersing for 20min by using a high-speed stirrer, and discharging;
(2) and (2) after controlling and stabilizing the temperature of each zone of the double-screw extruder at 230-250 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite polyamide material.
A polyamide film is composed of 10 parts by weight of the white graphene composite polyamide material and 90 parts by weight of PA6 resin.
The preparation method of the polyamide film comprises the following steps: after the temperature of each area of the film casting machine is stabilized at 220-240 ℃, the white graphene composite polyamide material and the PA6 resin are weighed and added into a material cylinder of the film casting machine, and the mixture is extruded and air-cooled, wherein the longitudinal stretching ratio is 300%, the longitudinal stretching heat setting temperature is 80%, the transverse stretching ratio is 350%, the transverse stretching heat setting temperature is 150 ℃, and then the polyamide film is obtained by rolling.
Example 2
In an embodiment of the white graphene composite polyamide material according to the present invention, a formula of the white graphene composite polyamide material according to the embodiment is shown in table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1 part by weight of 2-20 layers of white graphene is subjected to reflux treatment for 5 hours at a high temperature of 120 ℃ by using sulfuric acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the white graphene; then placing the mixture into an ethanol water solution, adding 10 parts by weight of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring the mixture at normal temperature for 5 hours, and washing unreacted KH590 on the surface of the white graphene for multiple times by using toluene; and finally, placing the white graphene with the chemically modified KH590 on the surface into deionized water dissolved with 40 parts by weight of acrylamide in advance, adding 5 parts by weight of photoinitiator 500, irradiating for 1h by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted acrylamide monomers on the surface of the white graphene for multiple times by using ethanol, and drying at 80 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite polyamide material comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 65 ℃, weighing PA6 resin, modified white graphene and PP-g-MAH in parts by weight, premixing and dispersing for 15min by using a high-speed mixer, and discharging;
(2) and (2) after controlling and stabilizing the temperature of each zone of the double-screw extruder at 230-250 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite polyamide material.
A polyamide film is composed of 5 parts by weight of the white graphene composite polyamide material and 95 parts by weight of PA66 resin.
The preparation method of the polyamide film comprises the following steps: after the temperature of each area of the film casting machine is stabilized at 220-250 ℃, the white graphene composite polyamide material and the PA66 resin are weighed and added into a material cylinder of the film casting machine, and the mixture is extruded and air-cooled, wherein the longitudinal stretching ratio is 350%, the longitudinal stretching heat setting temperature is 100 ℃, the transverse stretching ratio is 320%, the transverse stretching heat setting temperature is 120 ℃, and then the polyamide film is obtained by rolling.
Example 3
In an embodiment of the white graphene composite polyamide material according to the present invention, a formula of the white graphene composite polyamide material according to the embodiment is shown in table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1 part by weight of 2-20 layers of white graphene is subjected to reflux treatment for 5 hours at a high temperature of 100 ℃ by using mixed acid of nitric acid and sulfuric acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the white graphene; then placing the mixture into an ethanol water solution, adding 1 weight part of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 3 hours at normal temperature, and washing unreacted KH590 on the surface of the white graphene for multiple times by using acetone; and finally, placing the white graphene with the chemically modified KH590 on the surface into an ethanol solvent in which 20 parts by weight of acrylamide is dissolved in advance, adding 3 parts by weight of photoinitiator 184, irradiating for 1h by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted acrylamide monomers on the surface of the white graphene for multiple times by using deionized water, and drying at 90 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite polyamide material comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 90 ℃, weighing PA66 resin, modified white graphene and PP-g-MAH in parts by weight, premixing and dispersing for 10min by using a high-speed mixer, and discharging;
(2) and (2) after controlling the temperature of each zone of the double-screw extruder to be stable at 180-230 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite polyamide material.
A polyamide film was formed from 2 parts by weight of the white graphene composite polyamide material described in this example and 98 parts by weight of MXD6 resin.
The preparation method of the polyamide film comprises the following steps: after the temperature of each area of the film casting machine is stabilized at 210-250 ℃, the white graphene composite polyamide material and MXD6 resin are weighed and added into a material cylinder of the film casting machine, and the mixture is extruded and air-cooled, wherein the longitudinal stretching ratio is 280%, the longitudinal stretching heat setting temperature is 80%, the transverse stretching ratio is 320%, the transverse stretching heat setting temperature is 120 ℃, and then the mixture is rolled to obtain the polyamide film.
Example 4
In an embodiment of the white graphene composite polyamide material according to the present invention, a formula of the white graphene composite polyamide material according to the embodiment is shown in table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1 part by weight of 2-20 layers of white graphene is subjected to reflux treatment for 0.5h at a high temperature of 250 ℃ by nitric acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the white graphene; then placing the mixture into an ethanol water solution, adding 15 parts by weight of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 0.5h at normal temperature, and washing unreacted KH590 on the surface of the white graphene for multiple times by using acetone; and finally, placing the white graphene with the chemically modified KH590 on the surface into deionized water in which 50 parts by weight of acrylamide is dissolved in advance, adding 10 parts by weight of photoinitiator 1173, irradiating for 6 hours by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted acrylamide monomers on the surface of the white graphene for multiple times by using ethanol, and drying at 100 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite polyamide material is the same as that of the embodiment 1.
A polyamide film is composed of 10 parts by weight of the white graphene composite polyamide material and 90 parts by weight of PA6 resin.
The preparation method of the polyamide film is the same as that of example 1.
Example 5
In an embodiment of the white graphene composite polyamide material according to the present invention, a formula of the white graphene composite polyamide material according to the embodiment is shown in table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1 part by weight of 2-20 layers of white graphene is subjected to reflux treatment at a high temperature of 60 ℃ for 12 hours by using mixed acid of nitric acid and sulfuric acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the white graphene; then placing the mixture into an ethanol water solution, adding 0.5 weight part of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 6 hours at normal temperature, and washing unreacted KH590 on the surface of the white graphene for multiple times by using acetone; and finally, placing the white graphene with the chemically modified KH590 on the surface into deionized water in which 10 parts by weight of acrylamide is dissolved in advance, adding 0.5 part by weight of photoinitiator 1173, irradiating for 0.1h by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted acrylamide monomers on the surface of the white graphene for multiple times by using ethanol, and drying at 100 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite polyamide material is the same as that of the embodiment 1.
A polyamide film is composed of 1 part by weight of the white graphene composite polyamide material and 99 parts by weight of PA6 resin.
The preparation method of the polyamide film is the same as that of example 1.
Example 6
In an embodiment of the white graphene composite polyamide material according to the present invention, a formula of the white graphene composite polyamide material according to the embodiment is shown in table 1.
In this embodiment, the preparation method of the modified white graphene is the same as that in embodiment 1.
The preparation method of the white graphene composite polyamide material is the same as that of example 1.
A polyamide film is composed of 30 parts by weight of the white graphene composite polyamide material and 70 parts by weight of PA6 resin.
The preparation method of the polyamide film is the same as that of example 1.
Example 7
In an embodiment of the white graphene composite polyamide material according to the present invention, a formula of the white graphene composite polyamide material according to the embodiment is shown in table 1.
In this embodiment, the preparation method of the modified white graphene is the same as that in embodiment 1.
The preparation method of the white graphene composite polyamide material is the same as that of example 1.
A polyamide film is composed of 6 parts by weight of the white graphene composite polyamide material and 94 parts by weight of PA6 resin.
The preparation method of the polyamide film is the same as that of example 1.
Example 8
In an embodiment of the white graphene composite polyamide material according to the present invention, a formula of the white graphene composite polyamide material according to the embodiment is shown in table 1.
In this embodiment, the preparation method of the modified white graphene is the same as that in embodiment 1.
The preparation method of the white graphene composite polyamide material is the same as that of example 1.
A polyamide film is composed of 6 parts by weight of the white graphene composite polyamide material and 94 parts by weight of PA6 resin.
The preparation method of the polyamide film is the same as that of example 1.
Example 9
In an embodiment of the white graphene composite polyamide material according to the present invention, a formula of the white graphene composite polyamide material according to the embodiment is shown in table 1.
In this embodiment, the preparation method of the modified white graphene is the same as that in embodiment 1.
The preparation method of the white graphene composite polyamide material is the same as that of example 1.
A polyamide film is composed of 6 parts by weight of the white graphene composite polyamide material and 94 parts by weight of PA6 resin.
The preparation method of the polyamide film is the same as that of example 1.
Comparative example 1
The preparation method of the polyamide film according to the comparative example comprises the following steps:
after the temperature of each zone of the plastic film extruder is stabilized at 220-240 ℃, 100 parts of PA6 resin is weighed and added into a charging barrel of the plastic film extruder, and the PA6 film is obtained by extrusion and air cooling, wherein the longitudinal stretching ratio is 300%, the longitudinal stretching heat setting temperature is 80 ℃, the transverse stretching ratio is 350%, and the transverse stretching heat setting temperature is 150 ℃.
Comparative example 2
The preparation method of the polyamide film according to the comparative example comprises the following steps:
(1) and white graphene/MXD 6 resin premixing and dispersing: after the heating temperature of the high-speed mixer is stabilized at 80 ℃, 85 parts of MXD6, 10 parts of unmodified white graphene and 5 parts of PP-g-MAH are respectively weighed according to parts by weight and premixed and dispersed by a high-speed mixer for 20min to be discharged;
(2) and preparing the white graphene modified MXD6 master batch: after controlling the temperature of each zone of the double-screw extruder to be stable at 230-250 ℃, adding 100 parts of the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain white graphene modified MXD6 master batches;
(3) and preparing a white graphene composite PA6 film: after the temperature of each zone of the plastic film extruder is stabilized at 220-plus-240 ℃, 10 parts of white graphene modified MXD6 master batch and 90 parts of PA6 resin in the step 3) are weighed and added into a charging barrel of the plastic film extruder, and the white graphene composite PA6 film is obtained by extrusion, air cooling, wherein the longitudinal stretching ratio is 300%, the longitudinal stretching heat setting temperature is 80 ℃, the transverse stretching ratio is 350% and the transverse stretching heat setting temperature is 150 ℃ and then rolling.
Comparative example 3
The formula of the white graphene composite polyamide material in the comparative example is shown in table 1.
In this comparative example, the preparation method of the modified white graphene is the same as that of example 1.
The preparation method of the white graphene composite polyamide material is the same as that of example 1.
A polyamide film is composed of 6 parts by weight of the white graphene composite polyamide material and 94 parts by weight of PA6 resin.
The preparation method of the polyamide film is the same as that of example 1.
Table 1 formulations of white graphene composite polyamide materials described in examples 1 to 9 and comparative example 3
Example 10
The performance of the polyamide films described in examples 1 to 9 and comparative examples 1 to 3 was tested by the following method: puncture resistance according to ASTM D1709-04, gas and water vapor transmission according to GB/T1038-.
The test results are shown in Table 2.
TABLE 2 Properties of Polyamide films described in examples 1 to 9 and comparative examples 1 to 3
As can be seen from Table 2, the polyamide films of examples 1 to 9 are more transparent, have higher puncture strength, and have higher gas and water vapor barrier properties than those of comparative examples 1 to 3. With the increase of the addition amount of the modified white graphene, the transparency of the polyamide film is slightly influenced, the gas and water vapor barrier properties are greatly increased, but when the addition amount of the modified white graphene is increased to 15 parts, the tensile strength and the barrier properties are not greatly improved, but the cost is greatly increased, and when the addition amount is more than 20 parts, the puncture resistance strength of the modified white graphene is reduced to the level of the polyamide film prepared by a common method, and the modified white graphene is agglomerated to a certain extent, so that the cost is high.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The white graphene composite polyamide material is characterized by comprising the following components in parts by weight: 0.5-20 parts of modified white graphene, 60-99.4 parts of polyamide resin and 0.1-20 parts of compatilizer; the preparation method of the modified white graphene comprises the following steps:
(1) activating the white graphene under strong acid to obtain white graphene A;
(2) putting the white graphene A into an ethanol water solution, adding gamma-mercaptopropyl trimethoxysilane, stirring for reaction, taking out, and washing to obtain white graphene B;
(3) adding the white graphene B into a solvent in which an acrylamide monomer is dissolved, adding a photoinitiator, irradiating by ultraviolet light, taking out, washing and drying to obtain the modified white graphene;
wherein the white graphene, the gamma-mercaptopropyl trimethoxysilane, the acrylamide monomer and the photoinitiator are prepared from the following components in parts by weight: 1 part of white graphene, 0.5-15 parts of gamma-mercaptopropyl trimethoxy silane, 10-50 parts of acrylamide monomer and 0.5-10 parts of photoinitiator.
2. The white graphene composite polyamide material according to claim 1, wherein the modified white graphene is added in an amount of 1 to 15 parts by weight; the modified white graphene is 2-20 layers of modified white graphene.
3. The white graphene composite polyamide material according to claim 2, wherein the polyamide resin is 80 to 98.9 parts by weight, and the compatibilizer is 0.1 to 5 parts by weight.
4. The white graphene composite polyamide material according to claim 1, wherein at least one of the following (a) to (d):
(a) the strong acid species is nitric acid and/or sulfuric acid;
(b) in the step (3), the solvent used for dissolving the acrylamide monomer is at least one of deionized water, ethanol, propanol, isopropanol and butanol;
(c) the photoinitiator species is at least one of 250, 369, 184, 907, 500 and 1173 photoinitiators;
(d) the solvent adopted for washing is at least one of toluene, xylene, acetone, butanone and tetrahydrofuran.
5. The white graphene composite polyamide material according to claim 1, wherein the polyamide resin is at least one of PA6, MXD6, PA66, PA10, PA11, PA12, PA46, PA610, PA1010, and PA 612; the compatilizer is PP grafted maleic anhydride.
6. The preparation method of the white graphene composite polyamide material according to any one of claims 1 to 5, characterized by comprising the following steps:
(A) starting a high-speed mixer, heating to 60-120 ℃, weighing polyamide resin, modified white graphene and a compatilizer, and premixing and dispersing for 5-30 min by a high-speed disperser;
(B) and (3) starting the double-screw extruder, keeping the temperature of each zone at 210-280 ℃, adding the premixed and dispersed material obtained in the step (A) into a charging barrel of the double-screw extruder after the material is stabilized, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite polyamide material.
7. The polyamide film is characterized by comprising the following components in parts by weight: 1-30 parts of the white graphene composite polyamide material as claimed in any one of claims 1-5 and 70-99 parts of polyamide resin.
8. The method for producing a polyamide film according to claim 7, comprising the steps of: starting a film casting machine, wherein the temperature of each zone is 210-280 ℃, after the stability, adding the white graphene composite polyamide material and the polyamide resin into a material cylinder of the film casting machine, and obtaining the polyamide film through extrusion, air cooling, longitudinal and transverse bidirectional stretching, heat setting and rolling; the longitudinal stretching ratio is 250-400%, and the longitudinal stretching heat setting temperature is 60-120 ℃; the transverse stretching ratio is 300-450%, and the transverse stretching heat setting temperature is 120-180 ℃.
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