CN110845793B - High-barrier polypropylene/nylon composite material and preparation method thereof, high polymer material part and application thereof - Google Patents
High-barrier polypropylene/nylon composite material and preparation method thereof, high polymer material part and application thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract
The invention belongs to the field of high polymer material processing, and particularly relates to a high-barrier polypropylene/nylon composite material and a preparation method thereof, a high polymer material product and application thereof, wherein the high-barrier polypropylene/nylon composite material is prepared from the following raw materials: the composite material comprises, by weight, S1, polypropylene, 48-90%, S2, nylon, 2-20%, S3, graphene premix, 2-10%, S4, an elastomer, 5-20%, S5, a solubilizer, 1-10%, S6 and an auxiliary agent package. The graphene premix is prepared from the following raw materials: s3-1, graphene, S3-2, water, S3-3, latex, S3-4 and a flocculating agent. The polypropylene/nylon composite material obtained by the invention has higher barrier property, particularly has good barrier effect on small molecular gases (such as hydrogen and nitrogen), and simultaneously improves the wear resistance and the scratch resistance of the composite material.
Description
Technical Field
The invention belongs to the field of high polymer material processing, and particularly relates to a high-barrier polypropylene/nylon composite material, a preparation method thereof, a high polymer material product and application thereof.
Background
The polypropylene as a general thermoplastic plastic is widely applied to the fields of household appliances, automobile parts, daily necessities and the like due to the advantages of no toxicity, low price, small relative density, chemical corrosion resistance, high strength, easy recycling and the like. However, polypropylene has certain permeability to oxygen, carbon dioxide, water vapor and other gases, has poor barrier property, is not suitable for being used as a barrier material, and limits the application range and the increase of the additional value of polypropylene.
The nylon (PA) has the characteristics of excellent high and low temperature resistance, wear resistance, good barrier property and the like, and can be used for preparing parts such as oil pipelines and the like with higher barrier requirements. In addition, the arrangement mode of carbon atoms in the graphene adopts sp2 hybridization orbitals like a graphite monoatomic layer, the pore size of a carbon six-membered ring is only 0.15nm, the diameter of the carbon six-membered ring is smaller than the minimum gas molecular diameter (0.25 nm of helium), and the graphene has excellent gas barrier property.
Thus, there are many examples of modifying polypropylene to improve barrier properties. For example:
patent document CN 106346925 a discloses a nylon 6 modified polypropylene composite release film and a processing method thereof, wherein the five-layer co-extrusion layer structure comprises a first surface layer, a second toughening color matching layer, a third nylon 6 modified polypropylene reinforced barrier layer, a fourth toughening color matching layer and a fifth printing color matching layer in sequence, and can be used as a coiled material. Although the polypropylene composite film prepared by the method disclosed by the patent has good barrier property, the polypropylene composite film cannot well block small molecular gases (such as hydrogen), and meanwhile, the five-layer coextrusion reported by the patent has high requirements on forming equipment and a complex process.
Patent document CN 101633761 a discloses a barrier polypropylene composite material and a preparation method thereof, which uses polypropylene and ethylene-vinyl alcohol copolymer as raw materials, and utilizes the better gas barrier property of the ethylene-vinyl alcohol copolymer to improve the barrier property of the polypropylene, and simultaneously has better toughness. Since the patent only uses the barrier property of ethylene-vinyl alcohol, the barrier property is limited, and the patent cannot play a role in blocking small molecule gas (such as hydrogen).
Patent document CN 108099322 a discloses a graphene oxide-based high-barrier nanocomposite film and a preparation method thereof, wherein unmodified or silane-modified graphene oxide is used as a reinforcement, and is uniformly dispersed in a water-based or solvent-based adhesive by using an ultrasonic and stirring method, and then a middle film is formed between two layers of general films by using a dry-type compounding method to form the graphene oxide-based nanocomposite adhesive, so as to prepare the nanocomposite film. Since the patent adopts a preparation process of using graphene adhesive for adhesion between films, the shape and the application range of the product are limited, and the product with a complex shape is difficult to apply.
Patent document CN 108099322 a discloses a high-performance composite material composed of polypropylene, nylon 6 and graphene oxide and a preparation method thereof, wherein PA6 is grafted onto graphene oxide to obtain graphene oxide grafted nylon 6(GO-g-PA6), and then polypropylene grafted maleic anhydride (PP-g-MAH) is grafted to obtain graphene oxide grafted PA6-g-PP (GO-g-PA 6-g-PP). Finally, GO-g-PA6-g-PP is added into PP/PA6 to be used as a solubilizer to carry out high-shear melt blending to prepare the polypropylene/nylon 6/graphene oxide (PP/PA6/GO) nano composite material. However, the solubilizer reported in the patent is complex in preparation process, is not beneficial to industrial popularization, is low in graphene addition amount, and is not mentioned to be used as a barrier material.
Although the above-mentioned patent documents can prepare polypropylene composite materials with barrier properties, there are many problems that the barrier properties for small molecule gases (such as hydrogen and nitrogen) cannot be very good, or the requirements for processing equipment are high, the process molding is complicated, the application range is small, or the preparation process of the solubilizer is complicated.
Therefore, it is very important to develop a new path to prepare a polypropylene composite material capable of well blocking gas, especially small molecule gas (such as hydrogen).
Disclosure of Invention
The invention aims to provide a high-barrier polypropylene/nylon composite material and a preparation method thereof, a high-molecular material part and application thereof, aiming at solving the problem of the existing polypropylene composite material in the aspect of gas barrier modification.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in one aspect, a high barrier polypropylene/nylon composite is provided, which is prepared from the following raw materials:
s1, polypropylene, 48 to 90 wt% (e.g., 55 wt%, 63 wt%, 65 wt%, 70 wt%, 75 wt%, 82 wt%, 85 wt%), preferably 60 to 80 wt%;
s2, nylon, 2-20 wt% (e.g., 3 wt%, 6 wt%, 8 wt%, 12 wt%, 15 wt%, 18 wt%), preferably 5-10 wt%;
s3, graphene pre-mix, 2 to 10 wt% (e.g., 2.5 wt%, 3.5 wt%, 4 wt%, 6 wt%, 7 wt%, 9 wt%), preferably 3 to 8 wt%;
s4, elastomer, 5-20 wt% (e.g., 6 wt%, 8 wt%, 12 wt%, 14 wt%, 15 wt%, 18 wt%);
s5, a solubilizer, 1-10 wt% (e.g., 2 wt%, 3 wt%, 4 wt%, 6 wt%, 7 wt%, 9 wt%);
s6, an adjuvant package comprising: 0.01 wt% to 2 wt% (e.g., 0.02 wt%, 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.25 wt%, 0.5 wt%, 0.8 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%), preferably 0.2 wt% to 1 wt%, of a lubricant; 0.1 to 2 wt% (e.g., 0.15, 0.25, 0.5, 0.8, 1.2, 1.5, 1.8 wt%), preferably 0.2 to 1 wt%;
wherein each component is used in an amount based on the total weight (e.g., 100 wt%) of the polypropylene/nylon composite.
In some examples, the high barrier polypropylene/nylon composite is prepared from raw materials comprising the following components:
s1, 48-90 wt% of polypropylene;
s2, nylon 2-20 wt%;
s3, 2-10 wt% of graphene premix;
s4, elastomer, 5-20 wt%;
s5, and a solubilizer in an amount of 1-10 wt%;
s6, including: 0.01 to 2 weight percent of lubricant and 0.1 to 2 weight percent of antioxidant.
In some examples, the high barrier polypropylene/nylon composite is prepared from raw materials comprising the following components:
s1, 60-80 wt% of polypropylene;
s2, 5-10 wt% of nylon;
s3, 3-8 wt% of graphene premix;
s4, elastomer, 5-20 wt%;
s5, and a solubilizer in an amount of 1-10 wt%;
s6, including: 0.2 wt% -1 wt% of lubricant; 0.2 to 1 weight percent of antioxidant.
The above components are used in amounts based on the total weight (e.g., 100 wt%) of the polypropylene/nylon composite.
Graphene itself is a lamellar structure, which is not easily dispersed in a polymer due to its large specific surface area, small size, high surface energy, and thus easily agglomerated. In the preparation of the polypropylene/nylon composite material, when the graphene premix is used in an amount of less than 2 wt%, the obtained composite material cannot realize a barrier effect on small molecule gas (e.g., hydrogen); when the graphene pre-mixture is used in an amount of more than 10 wt%, it is liable to cause agglomeration of graphene in the composite material.
According to the polypropylene/nylon composite material provided by the invention, in some preferred embodiments, the graphene premix is prepared from raw materials comprising the following components:
s3-1, graphene,
s3-2, water,
s3-3, latex,
s3-4, flocculating agent;
wherein the mass ratio of graphene to water is 0.1: 100-5: 100 (e.g., 0.5:100, 0.8:100, 2:100, 2.5:100, 4:100), preferably 1: 100-3: 100;
the mass ratio of the latex to the water is 10:100 to 500:100 (for example, 15:100, 20:100, 50:100, 1:1, 150:100, 180:100, 250:100, 300:100, 400:100, 450:100), preferably 50:100 to 200: 100;
the amount of flocculant used is 0.5% to 2% (e.g., 0.8%, 1.2%, 1.4%, 1.8%) by mass of the latex, and preferably 1.0% to 1.5%.
In some preferred embodiments, the graphene pre-mix is prepared from raw materials comprising:
s3-1, graphene,
s3-2, water,
s3-3, latex,
s3-4, flocculating agent;
wherein the mass ratio of the graphene to the water is 0.1: 100-5: 100;
the mass ratio of the latex to the water is 10: 100-500: 100;
the dosage of the flocculating agent is 0.5 to 2 percent of the mass of the latex.
In some preferred embodiments, the graphene pre-mix is prepared from raw materials comprising:
s3-1, graphene,
s3-2, water,
s3-3, latex,
s3-4, flocculating agent;
wherein the mass ratio of the graphene to the water is 1: 100-3: 100;
the mass ratio of the latex to the water is 10: 100-500: 100;
the dosage of the flocculating agent is 0.5 to 2 percent of the mass of the latex.
In some preferred embodiments, the graphene pre-mix is prepared from raw materials comprising:
s3-1, graphene,
s3-2, water,
s3-3, latex,
s3-4, flocculating agent;
wherein the mass ratio of the graphene to the water is 0.1: 100-5: 100;
the mass ratio of the latex to the water is 50: 100-200: 100;
the dosage of the flocculating agent is 0.5 to 2 percent of the mass of the latex.
In the graphene premix, when the mass ratio of the latex to the water is less than 10:100, it is difficult to sufficiently disperse the graphene; when the mass ratio of the latex to water is more than 500:100, the gas barrier property of the composite material obtained by adding the latex to the system cannot be improved or even can be reduced.
In a preferred embodiment, the graphene is graphene oxide having a diameter of 0.2 to 10 μm (e.g., 0.6 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3.5 μm, 5 μm, 8 μm), more preferably 0.5 to 3 μm.
In some preferred embodiments, the latex is selected from one or more of an epoxidized natural rubber latex, a butadiene-pyridine latex, a carboxylated nitrile latex, a carboxylated styrene-butadiene latex, and a carboxylated polychloroprene latex. The graphene has the problem of difficult dispersion in the polymer and has poor compatibility with polypropylene, so that the dispersion is further difficult; therefore, the graphene latex premix is prepared by the latex firstly, so that the pre-dispersion of the graphene can be realized, and meanwhile, the compatibility of the graphene and the polypropylene can be improved by utilizing the latex, and the improvement of the toughness of the composite material is facilitated.
In some preferred embodiments, the flocculant is selected from anhydrous calcium chloride and/or aluminum sulfate.
In some examples, the graphene pre-mixture is prepared by: and adding graphene into water for ultrasonic dispersion, adding latex for stirring, adding a flocculating agent for flocculating out rubber in a reaction system, filtering, and drying to obtain the graphene premix with uniformly dispersed graphene.
In some examples, in the preparation method of the graphene premix, the process conditions of the ultrasonic dispersion include: the ultrasonic power is set to be 50-90%, and the ultrasonic time is 1-10 h.
In some examples, in the preparation method of the graphene pre-mixture, the stirring process conditions include: the rotating speed of the stirring paddle is 300-800 rpm, and the stirring time is 10-30 min.
In some examples, in the preparation method of the graphene pre-mixture, the process conditions of the drying treatment include: the drying temperature is 80-120 ℃, and the drying time is 1-3 h.
In some examples, the polypropylene is selected from homo-polypropylene and/or co-polypropylene, and the melt index of the polypropylene/nylon composite material is 0.1-100.
In some examples, the nylon is selected from one or more of nylon 6, nylon 12, a nylon of ternary, nylon 1010, and nylon 610.
In some examples, the elastomer is selected from one or more of ethylene octene copolymers, ethylene butene copolymers, ethylene propylene rubber, and SEBS.
In some examples, the solubilizer is selected from one or more of polypropylene grafted maleic anhydride, chlorinated polypropylene, chlorinated polyethylene, and POE grafted maleic anhydride.
In some examples, the lubricant is selected from one or more of calcium stearate, zinc stearate, magnesium stearate, white oil, and paraffin oil; the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant 626.
In another aspect, there is provided a method for preparing the polypropylene/nylon composite material, comprising the following steps:
(1) uniformly mixing the graphene premix with polypropylene, an elastomer, a solubilizer and an auxiliary agent package according to a ratio to obtain a mixture;
(2) and adding the obtained mixture into a main feeding port of a double-screw extruder, adding nylon into a side feeding port of the double-screw extruder, and performing extrusion granulation to obtain the polypropylene/nylon composite material.
According to the preparation method provided by the present invention, in some examples, the process conditions of step (1) include: the mixing time is 5-10 min, the rotating speed is 20-100 rpm, and the mixing temperature is 10-40 ℃.
In some examples, the extrusion process conditions of step (2) include: the screw temperature is 180-230 ℃, preferably 190-220 ℃, and the screw rotation speed is 200-900rpm, preferably 300-700 rpm.
According to the invention, the premix is prepared from the graphene and the latex, and the dispersion problem of the graphene in nylon and polypropylene and the compatibility problem of the polypropylene and the graphene are solved; on the basis, the barrier property of the polypropylene/nylon composite material is improved by utilizing the coordination effect of the nylon and the graphene. The prepared composite material has high barrier property, especially to small molecular gas (such as hydrogen), and the preparation process is simple. In addition, due to the introduction of the graphene and the nylon, the wear resistance of the polypropylene composite material is improved, and the application range of the composite material is further expanded.
The composite material utilizes the high barrier property of nylon to ensure that the nylon is uniformly dispersed in a polypropylene matrix to improve the barrier property of polypropylene; meanwhile, graphene with high barrier property is added, so that the barrier property of the polypropylene/nylon composite material is further improved, and the prepared polypropylene/nylon composite material has the characteristic of high barrier property. In addition, the application range of the material is expanded by utilizing different sensitivities of nylon and polypropylene to solvents, and the material has excellent barrier property to polar solvents and non-polar solvents. Meanwhile, the wear resistance and the scratch resistance of the composite material are improved. By utilizing the high barrier property of the graphene, the prepared composite material can be used for blocking various gases (especially small molecule gases such as hydrogen and nitrogen).
The barrier property of the invention is not only directed to small molecule gas, such as hydrogen, but also has better barrier property to other gases. It is worth noting that the composite material prepared by the invention has good barrier property particularly to small molecule gas.
In yet another aspect, a polymer material product is provided, which is prepared by using the polypropylene/nylon composite material as described above or the polypropylene/nylon composite material obtained by the preparation method as described above as raw material.
For high polymer material parts with high barrier property requirement in the processing process, the polypropylene/nylon composite material prepared by the invention can replace PP/PA, PE/EVOH/PA and other multilayer co-extruded materials.
In still another aspect, the invention also provides application of the high polymer material part in the fields of automobile pipelines, air storage tanks, air conveying pipes, food packaging materials and steam conveying.
The "%" appearing in the present invention means "% by weight" unless otherwise specified (except for ultrasonic power%).
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the graphene premix is prepared in advance and added into a polypropylene composite material system, so that the problem that graphene is difficult to disperse in a composite polymer is solved, and the graphene is well dispersed in a composite polymer matrix; meanwhile, the compatibility of the composite material can be improved;
2) the high-barrier polypropylene/nylon composite material can block polar solvents, non-polar solvents and various gases, and particularly has excellent barrier property on micromolecular gases; the nitrogen blocking coefficient is less than or equal to 0.05 x 10-14·cm2·s-1·Pa-1Hydrogen barrier coefficient less than or equal to 0.15 x 10-14·cm2·s-1·Pa-1；
3) Because the compatibility problem of the graphene with polypropylene and nylon is improved, and the problem that the graphene is easy to agglomerate in a polymer matrix is improved, the graphene is distributed in a lamellar manner in the polypropylene matrix, and the barrier property of the obtained composite material is improved;
4) the characteristics of good wear resistance and scratch resistance of nylon and graphene are utilized while the barrier property is improved, the wear resistance and scratch resistance of the polypropylene/nylon composite material are improved, and the Delta L after scraping is less than or equal to 1.0.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
In each of examples and comparative examples, the information on the raw materials used is as follows:
the twin screw extruder used was purchased from kyron Nanjing machines, Inc.
The test method comprises the following steps:
scratch resistance rating: the test was carried out according to standard PV3952, with a sample size of 90 x 55 x 3mm, a dermatoglyph number K09 and a test apparatus of the cross-wiper type 430P-I from ERICHSEN.
Gas permeability coefficient: the gas (such as nitrogen and hydrogen) barrier property test is carried out according to the ISO2782 standard by a self-made automatic gas tightness tester.
Example 1
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene HM671T, 73.79 wt%;
s2, nylon 610, 2 wt%;
s3, graphene premix, 2 wt%;
s4, 20 wt% of ethylene-butylene copolymer;
s5, chlorinated polypropylene, 2 wt%;
s6 and an auxiliary agent bag, wherein the weight percentage of calcium stearate is 0.01 percent; 0.1 wt% of antioxidant 1010 and 0.1 wt% of antioxidant 168.
The graphene premix is prepared from the following components:
s3-1, oxidized graphene with the diameter of 0.2-0.3 μm;
s3-2, deionized water;
s3-3, epoxy natural rubber latex;
s3-4, anhydrous calcium chloride;
the preparation method of the graphene premix comprises the following steps: firstly, adding graphene into deionized water for ultrasonic dispersion, wherein the ultrasonic power is set to be 50%, the ultrasonic time is 1h, and the mass ratio of the graphene to the deionized water is 0.1: 100; adding epoxy natural rubber latex after ultrasonic dispersion, and stirring, wherein the mass ratio of the latex to deionized water is 10:100, the rotating speed of a stirring paddle is 300rpm, and the stirring time is 10 min; and adding anhydrous calcium chloride to flocculate out the rubber in the reaction system, wherein the using amount of the anhydrous calcium chloride is 0.5 percent of the mass of the latex, the drying temperature is 80 ℃, and the drying time is 1h, so as to finally obtain the graphene premix with uniformly dispersed graphene.
The preparation method of the polypropylene/nylon composite material with high barrier property comprises the following specific steps:
(1) uniformly mixing the prepared graphene premix with polypropylene HM671T, chlorinated polypropylene, ethylene-butylene copolymer, calcium stearate, antioxidant 1010 and antioxidant 168 in a high-speed mixer according to a proportion to obtain a mixture, wherein the mixing time is 5min, the rotating speed is 50rpm, and the mixing temperature is 30 ℃.
(2) Adding the prepared mixture through a main feeding port of a double-screw extruder, adding nylon 610 through a side feeding port of the double-screw extruder, and carrying out melt mixing on the two materials in the double-screw extruder; the extrusion conditions were: the rotation speed of the screw is 300rpm, and the screw temperature is set to 180 ℃, 185 ℃, 190 ℃, 185 ℃ and 180 ℃ in a segmentation manner from the feed port to the machine head. Finally, the polypropylene/nylon composite material with high barrier property is prepared, and after the polypropylene/nylon composite material is processed into a sample, the performance of the polypropylene/nylon composite material is tested according to the test standards, and the test results are shown in table 1.
Comparative example 1
The components for preparing the graphene premix, the amounts thereof and the preparation steps are all referred to example 1.
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene HM671T, 75.79 wt%;
s3, graphene premix, 2 wt%;
s4, 20 wt% of ethylene-butylene copolymer;
s5, chlorinated polypropylene, 2 wt%;
s6 and an auxiliary agent bag, wherein the weight percentage of calcium stearate is 0.01 percent; 0.1 wt% of antioxidant 1010, 0.1 wt% of antioxidant 168,
nylon 610 is not added;
preparation of high barrier polypropylene/nylon composite the procedure was as in example 1.
After the polypropylene/nylon composite material with high barrier property is processed into a sample, the performance of the sample is tested according to the test standard, and the test results are shown in table 1.
Example 2
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene T30S, 69.4 wt%;
s2, nylon 12, 10 wt%;
s3, graphene premix, 5 wt%;
s4, 10 wt% of ethylene-octene copolymer;
s5, 5 wt% of polypropylene grafted maleic anhydride;
s6 and an auxiliary agent bag, wherein the weight percentage of zinc stearate is 0.2%; 0.2 wt% of antioxidant 1010 and 0.2 wt% of antioxidant 626.
The graphene premix is prepared from the following components:
s3-1, oxidized graphene with the diameter of 0.5-3 μm;
s3-2, deionized water;
s3-3, butyl Pimenta latex;
s3-4, aluminum sulfate;
the preparation method of the graphene premix comprises the following steps: firstly, adding graphene into deionized water for ultrasonic dispersion, wherein the ultrasonic power is set to be 70%, the ultrasonic time is 3 hours, and the mass ratio of the graphene to the deionized water is 1: 100; adding butadiene-pyridine latex after ultrasonic dispersion, and stirring, wherein the mass ratio of the latex to the deionized water is 20:100, the rotating speed of a stirring paddle is 500rpm, and the stirring time is 15 min; and adding aluminum sulfate to flocculate out the rubber in the reaction system, wherein the amount of the added aluminum sulfate is 1% of the mass of the latex, the drying temperature is 90 ℃, and the drying time is 1.5 hours, so as to finally prepare the graphene premix with uniformly dispersed graphene.
The preparation method of the polypropylene/nylon composite material with high barrier property comprises the following specific steps:
(1) uniformly mixing the prepared graphene premix with polypropylene T30S, ethylene-octene copolymer, polypropylene grafted maleic anhydride, zinc stearate, antioxidant 1010 and antioxidant 626 in a high-speed mixer according to a proportion to obtain a mixture, wherein the mixing time is 10min, the rotating speed is 20rpm, and the mixing temperature is 40 ℃.
(2) Adding the prepared mixture through a main feeding port of a double-screw extruder, adding nylon 12 through a side feeding port of the double-screw extruder, and carrying out melt mixing on the two materials in the double-screw extruder; the extrusion conditions were: the screw rotation speed is 500rpm, and the screw temperature is set at 190 deg.C, 200 deg.C, 220 deg.C, 210 deg.C, and 200 deg.C in stages from the feed port to the head. Finally, the polypropylene/nylon composite material with high barrier property is prepared, and after the polypropylene/nylon composite material is processed into a sample, the performance of the polypropylene/nylon composite material is tested according to the test standards, and the test results are shown in table 1.
Comparative example 2
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene T30S, 74.4 wt%;
s2, nylon 12, 10 wt%;
s4, 10 wt% of ethylene-octene copolymer;
s5, 5 wt% of polypropylene grafted maleic anhydride;
s6 and an auxiliary agent bag, wherein the weight percentage of zinc stearate is 0.2%; 0.2 wt% of antioxidant 1010 and 0.2 wt% of antioxidant 626.
No graphene premix was added.
Preparation procedure of high barrier polypropylene/nylon composite reference is made to example 2.
After the polypropylene/nylon composite material with high barrier property is processed into a sample, the performance of the sample is tested according to the test standard, and the test results are shown in table 1.
Example 3
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene BJ750, 66.1 wt%;
s2, nylon 6, 8 wt%;
s3, graphene premix, 6 wt%;
s4, ethylene propylene rubber, 15 wt%;
s5, chlorinated polyethylene, 3 wt%;
s6 and an auxiliary agent bag, wherein the white oil accounts for 1 wt%; 0.5 wt% of antioxidant 1076 and 0.4 wt% of antioxidant 168.
The graphene premix is prepared from the following components:
s3-1, oxidized graphene with the diameter of 10 μm;
s3-2, deionized water;
s3-3, carboxylic butyronitrile latex;
s3-4, anhydrous calcium chloride;
the preparation method of the graphene premix comprises the following steps: firstly, adding graphene into deionized water for ultrasonic dispersion, wherein the ultrasonic power is set to be 90%, the ultrasonic time is 10 hours, and the mass ratio of the graphene to the deionized water is 5: 100; adding carboxylic butyronitrile latex after ultrasonic dispersion for stirring, wherein the mass ratio of the latex to deionized water is 200:100, the rotating speed of a stirring paddle is 800rpm, and the stirring time is 30 min; and adding anhydrous calcium chloride to flocculate out the rubber in the reaction system, wherein the amount of the added anhydrous calcium chloride is 1.5% of the mass of the latex, the drying temperature is 120 ℃, and the drying time is 3 hours, so that the graphene premix with uniformly dispersed graphene is finally prepared.
The preparation method of the polypropylene/nylon composite material with high barrier property comprises the following specific steps:
(1) uniformly mixing the prepared graphene premix with polypropylene BJ750, ethylene propylene rubber, chlorinated polyethylene, antioxidant 1076, antioxidant 168 and white oil in a high-speed mixer according to a proportion to obtain a mixture, wherein the mixing time is 8min, the rotating speed is 60rpm, and the temperature is 10 ℃.
(2) Adding the prepared mixture through a main feeding port of a double-screw extruder, adding nylon 6 through a side feeding port of the double-screw extruder, and carrying out melt mixing on the two materials in the double-screw extruder; the extrusion conditions were: the screw rotation speed is 200rpm, and the screw temperature is set at 200 deg.C, 230 deg.C, 210 deg.C from the feed inlet to the head. Finally, the polypropylene/nylon composite material with high barrier property is prepared, and after the polypropylene/nylon composite material is processed into a sample, the performance of the polypropylene/nylon composite material is tested according to the test standards, and the test results are shown in table 1.
Example 4
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene EC340Q, 52.4 wt%;
s2, 20 wt% of ternary nylon;
s3, graphene premix, 10 wt%;
S4、SEBS，5wt％；
s5, 10 wt% of polypropylene grafted maleic anhydride;
s6 and an auxiliary agent bag, wherein the weight percentage of magnesium stearate is 0.6 percent, the weight percentage of antioxidant 1076 is 1 percent, and the weight percentage of antioxidant 626 is 1 percent.
The graphene premix is prepared from the following components:
s3-1, oxidized graphene with the diameter of 0.5-3 μm;
s3-2, deionized water;
s3-3, carboxylic styrene-butadiene latex;
s3-4, anhydrous calcium chloride;
the preparation method of the graphene premix comprises the following steps: firstly, adding graphene into deionized water for ultrasonic dispersion, wherein the ultrasonic power is set to be 80%, the ultrasonic time is 7 hours, and the mass ratio of the graphene to the deionized water is 5: 100; adding carboxylic styrene-butadiene latex after ultrasonic dispersion, and stirring, wherein the mass ratio of the latex to the deionized water is 500:100, the rotating speed of a stirring paddle is 800rpm, and the stirring time is 30 min; and adding anhydrous calcium chloride to flocculate out the rubber in the reaction system, wherein the amount of the added anhydrous calcium chloride is 2% of the mass of the latex, the drying temperature is 110 ℃, and the drying time is 2 hours, so that the graphene premix with uniformly dispersed graphene is finally prepared.
The preparation method of the polypropylene/nylon composite material with high barrier property comprises the following specific steps:
(1) and uniformly mixing the prepared graphene premix with polypropylene EC340Q, polypropylene grafted maleic anhydride, SEBS, antioxidant 1076, antioxidant 626 and magnesium stearate in a high-speed mixer according to a proportion to obtain a mixture, wherein the mixing time is 6min, the rotating speed is 70rpm, and the temperature is 20 ℃.
(2) Adding the prepared mixture through a main feeding port of a double-screw extruder, adding the ternary nylon through a side feeding port of the double-screw extruder, and carrying out melt mixing on the two materials in the double-screw extruder; the extrusion conditions were: the screw rotation speed is 900rpm, and the screw temperature is set at 185 deg.C, 190 deg.C, 210 deg.C, 190 deg.C, 185 deg.C, and 180 deg.C in stages from the feed inlet to the head. Finally, the polypropylene/nylon composite material with high barrier property is prepared, and after the polypropylene/nylon composite material is processed into a sample, the performance of the polypropylene/nylon composite material is tested according to the test standards, and the test results are shown in table 1.
Example 5
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene EP548RQ, 72.4 wt%;
s2, nylon 1010, 5 wt%;
s3, graphene premix, 8 wt%;
s4, 10 wt% of ethylene-octene copolymer;
s5, POE grafted maleic anhydride, 2 wt%;
s6 and an auxiliary agent package, wherein the paraffin oil accounts for 2 wt%, the antioxidant 1010 accounts for 0.3 wt%, and the antioxidant 168 accounts for 0.3 wt%.
The graphene premix is prepared from the following components:
s3-1, oxidized graphene with the diameter of 10 μm;
s3-2, deionized water;
s3-3, carboxyl neoprene latex;
s3-4, aluminum sulfate;
the preparation method of the graphene premix comprises the following steps: firstly, adding graphene into deionized water for ultrasonic dispersion, wherein the ultrasonic power is set to be 75%, the ultrasonic time is 3 hours, and the mass ratio of the graphene to the deionized water is 3: 100; adding carboxyl neoprene latex after ultrasonic dispersion, and stirring, wherein the mass ratio of the latex to deionized water is 400:100, the rotating speed of a stirring paddle is 600rpm, and the stirring time is 25 min; and adding aluminum sulfate to flocculate the rubber in the reaction system, wherein the adding amount of the aluminum sulfate is 1.5 percent of the mass of the latex, the drying temperature is 100 ℃, and the drying time is 3 hours, so as to finally prepare the graphene premix with uniformly dispersed graphene.
The preparation method of the polypropylene/nylon composite material with high barrier property comprises the following specific steps:
(1) uniformly mixing the prepared graphene premix with polypropylene EP548RQ, ethylene-octene copolymer, POE grafted maleic anhydride, antioxidant 1010, antioxidant 168 and paraffin oil in a high-speed mixer according to a proportion to obtain a mixture, wherein the mixing time is 5min, the rotating speed is 60rpm, and the temperature is 25 ℃.
(2) Adding the prepared mixture through a main feeding port of a double-screw extruder, adding nylon 1010 through a side feeding port of the double-screw extruder, and carrying out melt mixing on the two materials in the double-screw extruder; the extrusion conditions were: the screw rotation speed is 700rpm, and the screw temperature is set at 190 deg.C, 220 deg.C, 200 deg.C from the feed inlet to the head section. Finally, the high-barrier polypropylene/nylon composite material is prepared, and after the high-barrier polypropylene/nylon composite material is processed into a sample, the performance of the sample is tested according to the test standards, and the test results are shown in table 1.
Example 6
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene EP548RQ, 72.4 wt%;
s2, nylon 1010, 10 wt%;
s3, graphene premix, 3 wt%;
s4, 10 wt% of ethylene-octene copolymer;
s5, POE grafted maleic anhydride, 2 wt%;
s6 and an auxiliary agent package, wherein the paraffin oil accounts for 2 wt%, the antioxidant 1010 accounts for 0.3 wt%, and the antioxidant 168 accounts for 0.3 wt%.
The graphene premix is prepared from the following components:
s3-1, oxidized graphene with the diameter of 10 μm;
s3-2, deionized water;
s3-3, carboxyl neoprene latex;
s3-4, aluminum sulfate;
the preparation method of the graphene premix comprises the following steps: firstly, adding graphene into deionized water for ultrasonic dispersion, wherein the ultrasonic power is set to be 75%, the ultrasonic time is 3 hours, and the mass ratio of the graphene to the deionized water is 3: 100; adding carboxyl neoprene latex after ultrasonic dispersion, and stirring, wherein the mass ratio of the latex to deionized water is 50:100, the rotating speed of a stirring paddle is 600rpm, and the stirring time is 25 min; and adding aluminum sulfate to flocculate the rubber in the reaction system, wherein the adding amount of the aluminum sulfate is 1.5 percent of the mass of the latex, the drying temperature is 100 ℃, and the drying time is 3 hours, so as to finally prepare the graphene premix with uniformly dispersed graphene.
The preparation method of the polypropylene/nylon composite material with high barrier property comprises the following specific steps:
(1) uniformly mixing the prepared graphene premix with polypropylene EP548RQ, ethylene-octene copolymer, POE grafted maleic anhydride, antioxidant 1010, antioxidant 168 and paraffin oil in a high-speed mixer according to a proportion to obtain a mixture, wherein the mixing time is 5min, the rotating speed is 60rpm, and the temperature is 25 ℃.
(2) Adding the prepared mixture through a main feeding port of a double-screw extruder, adding nylon 1010 through a side feeding port of the double-screw extruder, and carrying out melt mixing on the two materials in the double-screw extruder; the extrusion conditions were: the screw rotation speed is 700rpm, and the screw temperature is set at 190 deg.C, 220 deg.C, 200 deg.C from the feed inlet to the head section. Finally, the high-barrier polypropylene/nylon composite material is prepared, and after the high-barrier polypropylene/nylon composite material is processed into a sample, the performance of the sample is tested according to the test standards, and the test results are shown in table 1.
Comparative example 3
The components for preparing the graphene premix, the amounts thereof and the preparation steps are all referred to example 1.
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene HM671T, 74.79 wt%;
s2, nylon 610, 2 wt%;
s3, graphene premix, 1 wt%;
s4, 20 wt% of ethylene-butylene copolymer;
s5, chlorinated polypropylene, 2 wt%;
s6 and an auxiliary agent bag, wherein the weight percentage of calcium stearate is 0.01 percent; 0.1 wt% of antioxidant 1010 and 0.1 wt% of antioxidant 168.
Preparation of high barrier polypropylene/nylon composite the procedure was as in example 1.
After the polypropylene/nylon composite material with high barrier property is processed into a sample, the performance of the sample is tested according to the test standard, and the test results are shown in table 1.
Comparative example 4
The components for preparing the graphene premix, the amounts thereof and the preparation steps are all referred to example 1.
The high-barrier polypropylene/nylon composite material comprises the following components in parts by weight:
s1, polypropylene HM671T, 60.79 wt%;
s2, nylon 610, 2 wt%;
s3, graphene premix, 15 wt%;
s4, 20 wt% of ethylene-butylene copolymer;
s5, chlorinated polypropylene, 2 wt%;
s6 and an auxiliary agent bag, wherein the weight percentage of calcium stearate is 0.01 percent; 0.1 wt% of antioxidant 1010 and 0.1 wt% of antioxidant 168.
Preparation of high barrier polypropylene/nylon composite the procedure was as in example 1.
After the polypropylene/nylon composite material with high barrier property is processed into a sample, the performance of the sample is tested according to the test standard, and the test results are shown in table 1.
Comparative example 5
The components, the using amount and the preparation steps of the high-barrier polypropylene/nylon composite material refer to example 1, and the difference is that:
the graphene premix is prepared from the following components:
s3-1, oxidized graphene with the diameter of 0.2-0.3 μm;
s3-2, deionized water;
s3-3, epoxy natural rubber latex;
s3-4, anhydrous calcium chloride. Wherein the mass ratio of the epoxidized natural rubber latex to the deionized water is 600: 100.
After the polypropylene/nylon composite material with high barrier property is processed into a sample, the performance of the sample is tested according to the test standard, and the test results are shown in table 1.
TABLE 1 results of Performance test of each example and comparative example
The test results in table 1 show that:
by preparing a graphene premix in advance and adding the graphene premix into a polypropylene composite material system, the problem that graphene is difficult to disperse in a polymer is solved, and graphene can be well dispersed in a polymer matrix; this gives the resulting polypropylene/nylon composite high barrier properties and good scratch resistance.
The high-barrier polypropylene/nylon composite material can block polar solvents, nonpolar solvents and various gases, and the gas barrier coefficient of the high-barrier polypropylene/nylon composite material to nitrogen is less than or equal to 0.05 x 10-14·cm2·s-1·Pa-1And a gas barrier coefficient against hydrogen of 0.15 x 10 or less-14·cm2·s-1·Pa-1。
The characteristics of good wear resistance and scratch resistance of nylon and graphene are utilized to improve the wear resistance and scratch resistance of the polypropylene/nylon composite material, and the Delta L after scraping is less than or equal to 1.0.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (13)
1. The high-barrier polypropylene/nylon composite material is characterized by being prepared from the following raw materials:
s1, 48-90 wt% of polypropylene;
s2, nylon 2-20 wt%;
s3, 2-10 wt% of graphene premix;
s4, elastomer, 5-20 wt%;
s5, and a solubilizer in an amount of 1-10 wt%;
s6, an adjuvant package comprising: 0.01 wt% -2 wt% of lubricant; 0.1 to 2 weight percent of antioxidant;
wherein, the amount of each component is based on the total weight of the polypropylene/nylon composite material;
the elastomer is selected from one or more of ethylene octene copolymer, ethylene butene copolymer, ethylene propylene rubber and SEBS; the solubilizer is selected from one or more of polypropylene grafted maleic anhydride, chlorinated polypropylene, chlorinated polyethylene and POE grafted maleic anhydride;
the graphene premix is prepared from the following raw materials:
s3-1, graphene,
s3-2, water,
s3-3, latex,
s3-4, flocculating agent;
wherein the mass ratio of the graphene to the water is 0.1: 100-5: 100; the mass ratio of the latex to the water is 10: 100-500: 100; the dosage of the flocculating agent is 0.5 to 2 percent of the mass of the latex;
the graphene is graphene oxide, and the latex is selected from one or more of epoxy natural rubber latex, butadiene-pyridine latex, carboxylic acrylonitrile butadiene latex, carboxylic styrene-butadiene latex and carboxylic chloroprene latex; the flocculant is selected from anhydrous calcium chloride and/or aluminum sulfate;
the preparation method of the graphene premix comprises the following steps: and adding graphene into water for ultrasonic dispersion, adding latex for stirring, adding a flocculating agent for flocculating out rubber in a reaction system, filtering, and drying to obtain the graphene premix with uniformly dispersed graphene.
2. The polypropylene/nylon composite material of claim 1, prepared from raw materials comprising:
s1, 60-80 wt% of polypropylene;
s2, 5-10 wt% of nylon;
s3, 3-8 wt% of graphene premix;
s4, elastomer, 5-20 wt%;
s5, and a solubilizer in an amount of 1-10 wt%;
s6, an adjuvant package comprising: 0.2 wt% -1 wt% of lubricant; 0.2 to 1 weight percent of antioxidant.
3. The polypropylene/nylon composite material according to claim 1, wherein in the graphene premix, the mass ratio of graphene to water is 1: 100-3: 100; the mass ratio of the latex to the water is 50: 100-200: 100; the dosage of the flocculating agent is 1.0-1.5 percent of the mass of the latex.
4. The polypropylene/nylon composite of claim 1, wherein the graphene has a diameter of 0.2-10 μm.
5. The polypropylene/nylon composite of claim 4, wherein the graphene has a diameter of 0.5-3 μm.
6. The polypropylene/nylon composite material according to claim 1, wherein in the preparation method of the graphene premix, the process conditions of the ultrasonic dispersion comprise: setting the ultrasonic power to be 50-90% and the ultrasonic time to be 1-10 h;
in the preparation method of the graphene premix, the stirring process conditions include: the rotating speed of the stirring paddle is 300-800 rpm, and the stirring time is 10-30 min;
in the preparation method of the graphene premix, the drying process conditions include: the drying temperature is 80-120 ℃, and the drying time is 1-3 h.
7. The polypropylene/nylon composite according to any one of claims 1 to 6, wherein the polypropylene is selected from homo-and/or co-polypropylene having a melt index of 0.1 to 100; and/or
The nylon is selected from one or more of nylon 6, nylon 12, ternary nylon, nylon 1010 and nylon 610; and/or
The lubricant is selected from one or more of calcium stearate, zinc stearate, magnesium stearate, white oil and paraffin oil; and/or
The antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant 626.
8. A method for preparing the polypropylene/nylon composite material according to any one of claims 1 to 7, comprising the steps of:
(1) uniformly mixing the graphene premix with polypropylene, an elastomer, a solubilizer and an auxiliary agent package according to a ratio to obtain a mixture;
(2) and adding the obtained mixture into a main feeding port of a double-screw extruder, adding nylon into a side feeding port of the double-screw extruder, and performing extrusion granulation to obtain the polypropylene/nylon composite material.
9. The method according to claim 8, wherein the process conditions of step (1) include: the mixing time is 5-10 min, the rotating speed is 20-100 rpm, and the mixing temperature is 10-40 ℃.
10. The method of claim 8, wherein the extrusion process conditions of step (2) include: the temperature of the screw is 180-230 ℃; the screw speed was 200-900 rpm.
11. The method of claim 10, wherein the extrusion process conditions of step (2) include: the temperature of the screw is 190 ℃ and 220 ℃; the screw rotation speed is 300-700 rpm.
12. A polymer material product prepared by using the polypropylene/nylon composite material according to any one of claims 1 to 7 or the polypropylene/nylon composite material obtained by the preparation method according to any one of claims 8 to 11 as a raw material.
13. The polymer material of claim 12 applied to the fields of automobile pipelines, air storage tanks and air pipes.
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| CN102050993A (en) * | 2010-12-10 | 2011-05-11 | 上海金发科技发展有限公司 | Flame-retardant PP/nylon corrugated tube composite material and preparation method thereof |
| CN102532629A (en) * | 2011-12-30 | 2012-07-04 | 北京化工大学 | Preparation method of completely peeled oxidation graphene/ rubber nanometer composite material |
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