CN109880230B - White graphene composite PP material, film and preparation method thereof - Google Patents
White graphene composite PP material, film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a white graphene composite PP material which comprises the following components in parts by weight: 0.1-15 parts of modified white graphene, 60-99.7 parts of PP resin, 0.1-10 parts of white oil and 0.1-15 parts of compatilizer. The invention also discloses a preparation method of the white graphene composite PP material, a PP film containing the white graphene composite PP material and a preparation method of the PP film. The modified white graphene is added into the white graphene composite PP material, so that good physical and chemical bonding effects between the white graphene and a PP matrix can be realized. The white graphene composite PP film obtained by effectively and cooperatively matching the biaxial stretching process has high strength, high wear resistance and high barrier property, is also of a transparent structure, does not need to be added with antioxidants and other auxiliaries to improve the aging resistance, simplifies the formula, and has wide application range and market prospect.
Description
Technical Field
The invention relates to a PP (polypropylene) material, and in particular relates to a white graphene composite PP material, a white graphene composite film and a preparation method of the white graphene composite PP material.
Background
Polypropylene (PP) is a thermoplastic resin prepared by polymerizing propylene, is one of five general-purpose plastics, has the advantages of low density, fatigue resistance, chemical corrosion resistance, stress cracking resistance, easy forming and processing and the like, and is widely applied to the industries of pipes, household appliances, films, automobile parts and the like.
Among them, PP films are widely used for packaging foods, pharmaceuticals, candies, cosmetics, and the like. The PP film is further widely applied due to the defects of low strength and elongation at break, easy scratching of the surface of a finished product, poor barrier property to oxygen and water vapor and the like. Therefore, the modification of PP materials to improve the strength and the barrier property is imperative.
In the past, inorganic particles are mostly used for modifying PP, but the compatibility with a PP resin matrix is poor, the mechanical strength and the wear resistance of the modified PP film can be improved, but the barrier property cannot be improved, and the PP film cannot be popularized and applied in the field of packaging. In some researches, the mechanical strength and the gas barrier property of the PP film can be improved by adopting the layered kaolin, the montmorillonite and the novel material graphene modified PP film, but the PP film cannot achieve the effect of uniform dispersion in a PP resin matrix, and the kaolin and montmorillonite modified PP film is dark red, the graphene modified PP film is black, cannot be transparent and is unacceptable to consumers.
Disclosure of Invention
The invention aims to overcome the defects of low strength and elongation at break, poor wear resistance, poor gas and water vapor barrier property and the like of a PP film on the market at present and provides a white graphene composite PP material, a film and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the white graphene composite PP material comprises the following components in parts by weight: 0.1-15 parts of modified white graphene, 60-99.7 parts of PP resin, 0.1-10 parts of white oil and 0.1-15 parts of compatilizer.
The white graphene composite PP material provided by the invention creatively uses the white graphene as a few-layered two-dimensional material, and a film prepared from the PP 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 15 parts, agglomeration is easy to occur, and the cost is high.
As a preferred embodiment of the white graphene composite PP material, 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 DMF solvent containing an acrylic monomer, 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 strong acid 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, and the purpose of washing is to remove the gamma-mercaptopropyl trimethoxysilane remained on the surface of the white graphene; the stirring reaction time is 0.5-6 h.
In the step (3), the time of ultraviolet irradiation is 0.1-6 h; the washing aims at washing off residual acrylic monomers on the surface of the white graphene, and the drying temperature is 30-120 ℃.
According to the modified white graphene, the acrylic acid high polymer is mildly, quickly, controllably and effectively chemically grafted on the surface of the white graphene by applying a novel mercapto-alkene click addition reaction, so that good compatibility with a polypropylene matrix is really realized, the modified white graphene can achieve good uniform dispersion in the PP matrix and can also generate covalent chemical bonding action with the PP matrix, and the generated bonding force is far greater than that of physical treatments such as simple filling, coating, adsorption and the like of other manufacturers on the market.
As a preferred embodiment of the white graphene composite PP material, the white graphene, the gamma-mercaptopropyl-trimethoxysilane, the acrylic acid 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 acrylic 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 PP material of the present invention, the white graphene, γ -mercaptopropyl-trimethoxysilane, an acrylic acid monomer, and a photoinitiator are prepared in parts by weight: 1 part of white graphene, 1-10 parts of gamma-mercaptopropyl-trimethoxysilane, 20-40 parts of acrylic monomers and 0.5-5 parts of photoinitiator. By adopting the raw material proportion, the prepared modified white graphene has better performance.
As a preferred embodiment of the white graphene composite PP material, the modified white graphene is added in an amount of 0.5 to 10 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 PP material, is easy to disperse, has no agglomeration phenomenon, and can ensure the performance of a PP film while controlling the production cost to be lower.
As a preferable embodiment of the white graphene composite PP material, the PP resin is 80-98.5 parts by weight, the white oil is 0.5-5 parts by weight, and the compatilizer is 0.5-10 parts by weight. When the proportion is adopted, the film prepared from the PP 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 PP 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) the acrylic monomer is at least one of acrylic acid, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, butyl acrylate, methyl methacrylate and glycidyl methacrylate;
(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 PP material, the PP resin is at least one of PP, PPR, PPB, and PPH; the white oil is at least one of 1#, 3#, 5#, 7#, 10#, 15#, 26#, 36#, 46# industrial grade white oil or food grade white oil; the compatilizer is PP grafted maleic anhydride.
The PP resin may be at least one of PP (polypropylene), PPR (random copolymer polypropylene), PPB (block copolymer polypropylene), and PPH (homo-polypropylene).
As a preferred embodiment of the white graphene composite PP material of the present invention, the PP resin is PP.
The invention also aims to provide a preparation method of the white graphene composite PP material, which comprises the following steps:
(A) starting a high-speed mixer to heat to 60-120 ℃, weighing the PP resin, the modified white graphene, the white oil and the compatilizer, and premixing and dispersing for 5-30 min by using a high-speed disperser;
(B) and (3) starting the double-screw extruder, controlling the temperature of each zone to be 170-230 ℃, the temperature of a machine head to be 180-240 ℃ and the rotating speed of a main machine to be 180-510 r/min, 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 PP material.
The invention also aims to provide a PP film which comprises the white graphene composite PP material.
As a preferred embodiment of the PP film of the present invention, the PP film comprises the following components in parts by weight: 1-10 parts of the white graphene composite PP material and 90-99 parts of PP resin.
As a preferred embodiment of the PP film of the present invention, the method for preparing the PP film comprises the following steps: starting a film casting machine, wherein the temperature of each zone is 170-240 ℃, the temperature of a casting die head is 180-250 ℃, after the film casting machine is stabilized, adding a white graphene composite PP material and PP resin into a material cylinder of the film casting machine, and obtaining the PP film through extrusion, casting, longitudinal and transverse bidirectional stretching, heat setting and rolling; the longitudinal stretching ratio is 160-350%, and the longitudinal stretching heat setting temperature is 60-120 ℃; the transverse stretching ratio is 300-380%, and the transverse stretching heat setting temperature is 100-160 ℃.
The modified white graphene and the PP 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 PP matrix in an oriented manner, and the effect of high barrier property to gas and water vapor can be achieved.
The invention has the beneficial effects that: the invention provides a white graphene composite PP material, a film and a preparation method thereof. The white graphene composite PP film obtained by effectively and cooperatively matching the biaxial stretching process has high strength, high wear resistance and high barrier property, is also of a transparent structure, does not need to be added with antioxidants and other auxiliaries to improve the aging resistance, simplifies the formula, and has wide application range and 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 PP material of the present invention, a formula of the white graphene composite PP material of the present 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 1.5 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 6 parts by weight 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 a DMF (dimethyl formamide) solvent in which 30 parts by weight of methyl acrylate is dissolved in advance, adding 1.5 parts by weight of photoinitiator 184, irradiating for 0.5h by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted methyl acrylate on the surface of the white graphene for multiple times by using tetrahydrofuran, and drying at 80 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite PP material comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 80 ℃, pre-mixing and dispersing PP resin, modified white graphene, No. 15 industrial white oil and PP grafted maleic anhydride (PP-g-MAH) for 5min by a high-speed mixer according to parts by weight, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 170-210 ℃, controlling the temperature of a machine head to be stable at 220 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 210r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite PP material.
A PP film, which consists of 6 parts by weight of the white graphene composite PP material and 94 parts by weight of PP resin.
The preparation method of the PP film comprises the following steps: after the temperature of each area of the film casting machine is started to be stabilized at 180-220 ℃, the temperature of the casting die head is controlled to be stabilized at 230 ℃, the white graphene composite PP material and the PP resin are weighed and added into a material cylinder of the film casting machine, and after extrusion and casting, 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 PP film is obtained through rolling.
Example 2
In an embodiment of the white graphene composite PP material of the present invention, a formula of the white graphene composite PP material of the present 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 1 hour at a high temperature of 120 ℃ 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 10 parts by weight of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring the mixture at normal temperature for 1.5 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 a DMF (dimethyl formamide) solvent in which 40 parts by weight of butyl acrylate is dissolved in advance, adding 5 parts by weight of a photoinitiator 250, irradiating for 1h by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted butyl acrylate on the surface of the white graphene for multiple times by using methylbenzene, and drying at 90 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite PP material comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 90 ℃, pre-mixing and dispersing PP resin, modified white graphene, 26# industrial white oil and PP-g-MAH in parts by weight for 10min by a high-speed mixer, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stabilized at 180-220 ℃, controlling the temperature of a machine head to be stabilized at 225 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 250r/min, and carrying out mixing, extrusion, water cooling, strip drawing and grain cutting to obtain the white graphene composite PP material.
A PP film, which consists of 6 parts by weight of the white graphene composite PP material and 94 parts by weight of PP resin.
The preparation method of the PP film comprises the following steps: after the temperature of each area of the film casting machine is started to be stabilized at 180-220 ℃, the temperature of the casting die head is controlled to be stabilized at 230 ℃, the white graphene composite PP material and the PP resin are weighed and added into a material cylinder of the film casting machine, and after extrusion and casting, 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 PP film is obtained through rolling.
Example 3
In an embodiment of the white graphene composite PP material of the present invention, a formula of the white graphene composite PP material of the present 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 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 a DMF (dimethyl formamide) solvent dissolved with 20 parts by weight of glycidyl acrylate in advance, adding 3 parts by weight of a photoinitiator 1173, irradiating by using ultraviolet light for 1.5h, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted glycidyl acrylate on the surface of the white graphene for multiple times by using tetrahydrofuran, and drying at 80 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite PP material comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 90 ℃, weighing PP resin, modified white graphene, 36# food-grade white oil and PP-g-MAH in parts by weight, premixing and dispersing for 15min by using a high-speed mixer, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 180-230 ℃, controlling the temperature of a machine head to be stable at 235 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 450r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite PP material.
A PP film is composed of 2 parts by weight of the white graphene composite PP material and 98 parts by weight of PP resin.
The preparation method of the PP film comprises the following steps: after the temperature of each area of the film casting machine is started and stabilized at 190-240 ℃ and the temperature of the casting die head is controlled and stabilized at 245 ℃, the white graphene composite PP material and the PP resin are weighed and added into a material cylinder of the film casting machine, and after extrusion and casting, the longitudinal stretching ratio is 200%, the longitudinal stretching heat setting temperature is 120 ℃, the transverse stretching ratio is 320%, the transverse stretching heat setting temperature is 160 ℃, and then the PP film is obtained through rolling.
Example 4
In an embodiment of the white graphene composite PP material of the present invention, a formula of the white graphene composite PP material of the present 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 a DMF (dimethyl formamide) solvent in which 50 parts by weight of methyl acrylate is dissolved in advance, adding 10 parts by weight of a photoinitiator 1173, irradiating for 6 hours by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted methyl acrylate on the surface of the white graphene for multiple times by using toluene, and drying at 100 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite PP material is the same as that of the embodiment 1.
A PP film is composed of 10 parts by weight of the white graphene composite PP material and 90 parts by weight of PP resin.
The PP film was prepared in the same manner as in example 1.
Example 5
In an embodiment of the white graphene composite PP material of the present invention, a formula of the white graphene composite PP material of the present 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 12 hours at a high temperature of 60 ℃ 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 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 a DMF (dimethyl formamide) solvent in which 10 parts by weight of methyl acrylate is dissolved in advance, adding 0.5 part by weight of a photoinitiator 1173, irradiating for 0.1h by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted methyl acrylate on the surface of the white graphene for multiple times by using methylbenzene, and drying at 100 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite PP material is the same as that of the embodiment 1.
A PP film is composed of 1 part by weight of the white graphene composite PP material and 99 parts by weight of PP resin.
The PP film was prepared in the same manner as in example 1.
Example 6
In an embodiment of the white graphene composite PP material of the present invention, a formula of the white graphene composite PP material of the present 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 PP material is the same as that of example 1.
A PP film, which consists of 6 parts by weight of the white graphene composite PP material and 94 parts by weight of PP resin.
The preparation method of the PP film is the same as that of example 1.
Example 7
In an embodiment of the white graphene composite PP material of the present invention, a formula of the white graphene composite PP material of the present 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 PP material is the same as that of example 1.
A PP film, which consists of 6 parts by weight of the white graphene composite PP material and 94 parts by weight of PP resin.
The preparation method of the PP film is the same as that of example 1.
Example 8
In an embodiment of the white graphene composite PP material of the present invention, a formula of the white graphene composite PP material of the present 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 PP material is the same as that of example 1.
A PP film, which consists of 6 parts by weight of the white graphene composite PP material and 94 parts by weight of PP resin.
The preparation method of the PP film is the same as that of example 1.
Example 9
In an embodiment of the white graphene composite PP material of the present invention, a formula of the white graphene composite PP material of the present 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 PP material is the same as that of example 1.
A PP film, which consists of 6 parts by weight of the white graphene composite PP material and 94 parts by weight of PP resin.
The preparation method of the PP film is the same as that of example 1.
Comparative example 1
The preparation method of the PP film described in this comparative example includes the following steps:
(1) PP resin premixing and dispersing: after the heating temperature of the high-speed mixer is stabilized at 80 ℃, 95 parts of PP resin, 1.5 parts of montmorillonite, 1.5 parts of phenol antioxidant 1010 and 2 parts of polyethylene wax are respectively weighed according to parts by weight and premixed and dispersed for 6min by a high-speed mixer to be discharged;
(2) and preparing a PP material: and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 170-210 ℃, controlling the temperature of a machine head to be stable at 220 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 250r/min, and carrying out mixing, extrusion, water cooling, strip drawing and grain cutting to obtain the PP material.
(3) And preparing a PP film: and (2) starting the film casting machine to stabilize the temperature of each area at 180-210 ℃, controlling the temperature of a casting die head to stabilize at 230 ℃, weighing 6 parts of PP material and 94 parts of PP resin in the step (2), adding the PP material and the PP resin into a material cylinder of the film casting machine, extruding and casting, 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 rolling to obtain the PP film.
Comparative example 2
The preparation method of the PP film described in this comparative example includes the following steps:
(1) and premixing and dispersing white graphene/PP resin: after the heating temperature of a high-speed mixer is stabilized at 80 ℃, 95 parts of PP resin, 1.5 parts of unmodified white graphene, 1.5 parts of No. 15 industrial white oil and 2 parts of polyethylene wax are weighed according to parts by weight and premixed and dispersed for 6min by a high-speed mixer, and then discharged;
(2) and preparing a PP material: and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 170-210 ℃, controlling the temperature of a machine head to be stable at 220 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 250r/min, and carrying out mixing, extrusion, water cooling, strip drawing and grain cutting to obtain the PP material.
(3) And preparing a PP film: and (2) starting the film casting machine to stabilize the temperature of each area at 180-220 ℃, controlling the temperature of a casting die head to stabilize at 230 ℃, weighing 6 parts of PP material and 94 parts of PP resin in the step (2), adding the PP material and the PP resin into a material cylinder of the film casting machine, extruding and casting, 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 rolling to obtain the PP film.
Comparative example 3
The formula of the white graphene composite PP material in the comparative example is shown in the 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 PP material is the same as that of example 1.
A PP film, which consists of 6 parts by weight of the white graphene composite PP material and 94 parts by weight of PP resin.
The preparation method of the PP film is the same as that of example 1.
Table 1 formulations of white graphene composite PP materials described in examples 1 to 9 and comparative example 3
Example 10
The PP films of examples 1-9 and comparative examples 1-3 were tested for performance by the following methods: tensile strength according to ISO 527-2: 1993, the gas and water vapor transmission rate is according to the GB/T1038-.
The test results are shown in Table 2.
TABLE 2 Properties of PP films described in examples 1 to 9 and comparative examples 1 to 3
As can be seen from Table 2, the PP films of examples 1 to 9 are more transparent, have higher tensile 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 PP film is slightly less affected, and the gas and water vapor barrier properties are greatly increased, but when the addition amount of the modified white graphene is increased to 5 parts, the tensile strength of the modified white graphene is reduced to a certain extent, and when the addition amount is more than 15 parts, the tensile strength of the modified white graphene is reduced to the level of the PP film prepared by the 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 (10)
1. The white graphene composite PP material is characterized by comprising the following components in parts by weight: 0.1-15 parts of modified white graphene, 60-99.7 parts of PP resin, 0.1-10 parts of white oil and 0.1-15 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 DMF (dimethyl formamide) solvent containing an acrylic monomer, adding a photoinitiator, irradiating by ultraviolet light, taking out, washing and drying to obtain the modified white graphene;
the acrylic monomer is at least one of acrylic acid, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, butyl acrylate, methyl methacrylate and glycidyl methacrylate.
2. The white graphene composite PP material of claim 1, wherein the white graphene, the gamma-mercaptopropyltrimethoxysilane, the acrylic 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 acrylic monomers and 0.5-10 parts of photoinitiator.
3. The white graphene composite PP material of claim 1, wherein the modified white graphene is added in an amount of 0.5 to 10 parts by weight; the modified white graphene is 2-20 layers of modified white graphene.
4. The white graphene composite PP material according to claim 3, wherein the PP resin is 80 to 98.5 parts by weight, the white oil is 0.5 to 5 parts by weight, and the compatibilizer is 0.5 to 10 parts by weight.
5. The white graphene composite PP material according to claim 1, wherein at least one of the following (a), (c) and (d):
(a) the strong acid species is nitric acid and/or sulfuric acid;
(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.
6. The white graphene composite PP material of claim 1, wherein the PP resin is at least one of PP, PPR, PPB and PPH; the white oil is at least one of 1#, 3#, 5#, 7#, 10#, 15#, 26#, 36#, 46# industrial grade white oil or food grade white oil; the compatilizer is PP grafted maleic anhydride.
7. The white graphene composite PP material of claim 6, wherein the PP resin is PP.
8. The preparation method of the white graphene composite PP material according to any one of claims 1 to 7, comprising the following steps:
(A) starting a high-speed mixer to heat to 60-120 ℃, weighing the PP resin, the modified white graphene, the white oil and the compatilizer, and premixing and dispersing for 5-30 min by using a high-speed disperser;
(B) and (3) starting the double-screw extruder, controlling the temperature of each zone to be 170-230 ℃, the temperature of a machine head to be 180-240 ℃ and the rotating speed of a main machine to be 180-510 r/min, 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 PP material.
9. The PP film is characterized by comprising the following components in parts by weight: 1-10 parts of the white graphene composite PP material as claimed in any one of claims 1-7 and 90-99 parts of PP resin.
10. The method for preparing a PP film according to claim 9, wherein the method for preparing a PP film comprises the steps of: starting a film casting machine, wherein the temperature of each zone is 170-240 ℃, the temperature of a casting die head is 180-250 ℃, after the film casting machine is stabilized, adding a white graphene composite PP material and PP resin into a material cylinder of the film casting machine, and obtaining the PP film through extrusion, casting, longitudinal and transverse bidirectional stretching, heat setting and rolling; the longitudinal stretching ratio is 160-350%, and the longitudinal stretching heat setting temperature is 60-120 ℃; the transverse stretching ratio is 300-380%, and the transverse stretching heat setting temperature is 100-160 ℃.
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