CN114874526A - High-barrier composite material and preparation method thereof - Google Patents
High-barrier composite material and preparation method thereof Download PDFInfo
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- CN114874526A CN114874526A CN202210485473.XA CN202210485473A CN114874526A CN 114874526 A CN114874526 A CN 114874526A CN 202210485473 A CN202210485473 A CN 202210485473A CN 114874526 A CN114874526 A CN 114874526A
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 26
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 24
- 239000003502 gasoline Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012745 toughening agent Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 239000000155 melt Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 21
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
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- 239000002245 particle Substances 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 claims description 5
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
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- 239000005022 packaging material Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- MLJRLEGXZUNRLY-UHFFFAOYSA-N 2,4-ditert-butylphenol;phosphorous acid Chemical compound OP(O)O.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 MLJRLEGXZUNRLY-UHFFFAOYSA-N 0.000 claims description 2
- BBJZBUKUEUXKDJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[1-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoylamino]hexyl]propanamide Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1CCC(=O)NC(CCCCC)NC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BBJZBUKUEUXKDJ-UHFFFAOYSA-N 0.000 claims description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 2
- 239000002828 fuel tank Substances 0.000 claims description 2
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- 230000005484 gravity Effects 0.000 claims description 2
- 238000010102 injection blow moulding Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
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- 239000003337 fertilizer Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 16
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 239000010408 film Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
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- 241001521809 Acoma Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229920006021 bio-based polyamide Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
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- 229920006351 engineering plastic Polymers 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Abstract
The invention relates to a high-barrier composite material and a preparation method thereof, wherein the high-barrier composite material is prepared from the following raw materials in parts by weight: 20-99 parts of HDPE resin, 40-60 parts of MPA resin, 0.1-20 parts of compatilizer, 0.1-15 parts of nano graphite micro-sheet, 0.05-5 parts of silane coupling agent and 0.2-1.0 part of antioxidant, wherein the MPA resin is prepared from the following raw materials in parts by weight by adopting a melt extrusion process: 59-99 parts of PA6 resin, 0.1-40 parts of toughening agent, 0.2-1.0 part of initiator and 0.2-1.0 part of antioxidant. The high-barrier composite material has high barrier property to various solvents and gases, can be applied to packaging of easily-leaked articles such as pesticides, medicines, gasoline and the like, and has a wide application range.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a high-barrier composite material and a preparation method thereof.
Background
The application of high polymer materials in the field of packaging is more and more extensive. The syringe needle is as small as one needle, and the syringe needle is as large as the package of tank instruments, warships and equipment. However, for packaging of easily leaking articles such as pesticides, pharmaceuticals, gasoline, etc., single homopolymers and copolymers are often difficult to meet. In order to improve the barrier property of high polymer materials such as HEPE and the like, multilayer co-extrusion compounding is adopted at home and abroad. The preparation of barrier polymer materials by alloying methods is a new direction for research and development at home and abroad at present. Therefore, the development of the blending type barrier polymer packaging material has important practical application value.
High Density Polyethylene (HDPE) is a preferred ideal material for the packaging industry because it is non-toxic, inexpensive, lightweight, excellent moisture resistant, chemically stable, low temperature tough, easy to form and process, and has good optical properties. But its application range is greatly limited due to its high permeability to hydrocarbon solvents.
Nylon (PA) is one of important engineering plastics, has high strength, good heat resistance and wear resistance, and has been widely used in the production of industrial, electrical and automotive parts and the like. And its excellent properties of blocking oil olefin solvents make PA advantageous in the packaging field. However, nylon cannot be processed by blow molding, and thus cannot be made into products having distinctive shapes, such as tanks, buckets, and the like.
Patent application CN110982259A discloses a completely biodegradable high-barrier polyamide-based composite film material, which is composed of the following raw materials: biological polyamide material, glass fiber, water-soluble high-hydroxyl-density polymer, ultrapure water, nano inorganic matter, flatting agent and high molecular dispersing agent. According to the scheme, polyamide is introduced, and the permeability resistance of the base material layer is improved. The preparation method comprises the following steps: s1, preparation of coating liquid: putting one third of ultrapure water into a stirrer, heating to 92-96 ℃ in a water bath, pouring the water-soluble high-hydroxyl-density polymer into the stirrer, stirring for 20-30min to obtain a solution of the water-soluble high-hydroxyl-density high-molecular polymer, naturally cooling the solution to 35-45 ℃, adding the leveling agent and the high-molecular dispersing agent into the stirrer, and stirring for 25-35min to obtain a coating liquid for later use; s2, preparation of base materials: mixing a bio-based polyamide material, a nano inorganic substance and 40% of ultrapure water, stirring and reacting for 1.5-2.5h by using a magnetic stirrer, then cleaning by using ultrapure water, cleaning for 1-3 times by using acetone, removing impurities in the material, putting the material into a vacuum drying box, slowly and continuously raising the temperature to 85-95 ℃, drying until the water content is less than 0.5%, putting the dried base material into a grinder for grinding, and sieving by using a 200-mesh sieve to remove large particles to obtain fine particles; s3, extrusion casting: extruding the fine particles obtained in the step S2 through a screw extruder, respectively stretching the fine particles for three times in the longitudinal direction and the transverse direction through a casting machine, stretching the fine particles in the longitudinal direction and the transverse direction in a staggered manner, wherein the stretching ratio is 5-10% of the original length each time, and cooling to obtain a base material film; s4, coating: and (4) uniformly coating the coating liquid obtained in the step (S1) on two surfaces of the base material film, and drying to obtain the completely biodegradable high-barrier polyamide composite film. It can be seen that the preparation steps are long in flow, the production period is long, and the industrial production is not facilitated.
Disclosure of Invention
The invention aims to overcome the problem of poor barrier property of the existing composite material, and provides a high-barrier composite material, which can effectively combine HDPE, PA and nano-graphite micro-sheets by combining the barrier property of HDPE/PA/nano-graphite micro-sheets and adopting a proper compatibilization method to prepare the composite material with a laminated structure, and has the advantage of high barrier property to various solvents and gases.
The nano graphite microchip, also called graphene microchip, is a novel conductive material. It maintains the crystal structure, conductivity, stability and other properties of natural graphite, and has very large shape ratio (diameter to thickness ratio) to form laminated structure easily in plastic. Typically, nanographitic micro-slabs are used to form conductive thin films. The inventor believes that the stability of the nano graphite micro-sheet can effectively prevent certain substances such as oxygen, carbon dioxide and organic solvents from permeating and leaking, and therefore, the nano graphite micro-sheet can help to improve the barrier property of the material.
However, the introduction of nano graphite micro-sheets can cause the toughness of polyethylene to be rapidly reduced, the material becomes brittle, and a product with good application performance is difficult to obtain. Therefore, the inventor continuously finds out that the composite material with high barrier and high toughness is finally obtained by combining HDPE, PA and nano graphite micro-sheets under the comprehensive action of a compatilizer, a flexibilizer and the like.
The specific scheme is as follows:
the high-barrier composite material is prepared from the following raw materials in parts by weight: 20-99 parts of HDPE resin, 40-60 parts of MPA resin, 0.1-20 parts of compatilizer, 0.1-15 parts of nano graphite micro-sheet, 0.05-5 parts of silane coupling agent and 0.2-1.0 part of antioxidant, wherein the MPA resin is prepared from the following raw materials in parts by weight by adopting a melt co-extrusion process: 59-99 parts of PA6 resin, 0.1-40 parts of toughening agent, 0.2-1.0 part of initiator and 0.2-1.0 part of antioxidant.
Further, the high-barrier composite material is prepared from the following raw materials in parts by weight: 50-80 parts of HDPE resin, 40-60 parts of MPA resin, 10-20 parts of compatilizer, 3-15 parts of nano graphite micro-sheet, 1-4 parts of silane coupling agent and 0.2-1.0 part of antioxidant.
Further, the HDPE resin has a melt index of 0.01-0.05g/10min and a Shore hardness of 65-79D, and the compatilizer is one or more of HDPE-MAH, HDPE-GMA, POE-MAH and POE-MAH;
optionally, the antioxidant is selected from one or more of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] tetraethoester and tri (2, 4-di-tert-butylphenol) phosphite;
optionally, the nano graphite micro-sheet has a size of 3-6um and a thickness of<15nm, specific surface area of 40-60m 2 /g。
Further, the MPA resin is prepared from the following raw materials in parts by weight by adopting a melt co-extrusion process: 60-80 parts of PA6 resin, 10-30 parts of toughening agent, 0.2-1.0 part of initiator and 0.2-1.0 part of antioxidant;
optionally, the PA6 resin has a melting point of 220-230 ℃, a relative viscosity of 2.0-2.7 and a specific gravity of 1.13-1.14g/cm 3 。
Further, the toughening agent is one or more of EPDM, EMA and EMAA;
optionally, the initiator is an organic peroxide, preferably one or more of BIBP, DTBP, DHBP and TBPB.
Further, the absorption rate of the high-barrier composite material to gasoline after being soaked in the gasoline for 36 hours is lower than 1 wt%.
The invention also provides a preparation method of the high-barrier composite material, which comprises the following steps:
a) weighing raw materials according to the weight parts, premixing the PA6 resin, the toughening agent and the initiator in a mixer, adding the antioxidant, and continuously stirring to obtain a mixture;
b) and (3) placing the mixture in a double-screw extruder, and performing melt blending, extrusion and granulation to obtain the MPA resin.
c) Adding the MPA resin, the HDPE resin, the compatilizer and the coupling agent into a high-speed mixer for premixing, adding the nano graphite micro-sheets and the antioxidant, and continuing stirring to obtain a resin mixture;
d) and (3) placing the resin mixture in a double-screw extruder, and performing melt blending, extrusion and granulation to obtain the high-barrier composite material.
Further, in the step a), the dried PA6 resin, the toughening agent and the initiator are premixed in a low-speed mixer for 3-5 min, and then the antioxidant is added and continuously stirred for 5-10 min to obtain a mixture;
in the step b), the mixture is placed in a feeding section of a double-screw extruder, and the mixture is melted and blended by the double-screw extruder through a first section to a ninth section of the double-screw extruder, and then is extruded from a die head, pulled into strips and cut into particles; wherein the temperatures of the first section to the ninth section of the double-screw extruder are as follows in sequence: 180 to 200 ℃, 190 to 210 ℃, 200 to 230 ℃, 210 to 240 ℃, 220 to 250 ℃, 230 to 260 ℃; the die head temperature of the double-screw extruder is 230-270 ℃; the rotating speed of the main machine of the double-screw machine is 300-500 r/min; feeding frequency is 8-20 Hz;
in the step c), adding the MPA resin, the HDPE resin, the compatilizer and the coupling agent into a high-speed mixer for premixing for 3-5 min, adding the nano-graphite micro-sheets and the antioxidant, and continuing stirring for 5-10 min to obtain a resin mixture;
in the step d), the resin mixture is placed in a feeding section of a double-screw extruder, and the materials are melted and blended by the double-screw extruder, extruded from a die head, pulled into strips and cut into granules after passing through a first section to a ninth section of the double-screw extruder; wherein the temperatures of the first section to the ninth section of the double-screw extruder are as follows in sequence: 120 to 150 ℃, 130 to 170 ℃, 140 to 190 ℃, 150 to 200 ℃, 160 to 210 ℃, 170 to 220 ℃, 180 to 230 ℃ and 180 to 240 ℃; the die head temperature of the double-screw extruder is 220-250 ℃; the rotating speed of the main machine of the double-screw machine is 300-500 r/min; the feeding frequency is 8-20 Hz.
The invention also discloses a film material or a sheet material, which is obtained by drying the high-barrier composite material and then performing injection molding or blow molding, wherein the film material or the sheet material has an absorption rate of less than 1 wt% on gasoline after being soaked in the gasoline for 36 hours.
The invention also protects the application of the high-barrier composite material in packaging materials, automobile fuel tanks and oil pipelines.
Has the advantages that:
according to the invention, the nano-graphite micro-sheets are added in the formula, the barrier effect of the material is improved by utilizing the stability and the layered structure of the nano-graphite micro-sheets, and the barrier property of the composite material to an olefin solvent is further improved by adding MPA6, and on the other hand, the toughness of the composite material can be effectively improved by containing the toughening agent in MPA6, so that the application range of the composite material is wider, and the popularization and use in a wider range in the later period are facilitated.
Detailed Description
The definitions of some of the terms used in the present invention are given below, and other non-mentioned terms have definitions and meanings known in the art:
HDPE resin: high density polyethylene, HDPE in the invention, in the specific embodiment, the preferable model is one or more of LG-DOW/PB150, HHMTR-140, BA50-10, the melt index of the HDPE is 0.01-0.05g/10min, and the Shore hardness is 65-79D.
PA6 resin: a nylon resin.
MPA resin: the MPA resin is a blend formed by adding a toughening agent into nylon resin serving as a raw material, and is prepared from the following raw materials in parts by weight by adopting a melt co-extrusion process: 59-99 parts of PA6 resin, 0.1-40 parts of toughening agent, 0.2-1.0 part of initiator and 0.2-1.0 part of antioxidant. The PA6 resin is added with the blend of the toughening agent and the peroxide crosslinking agent, the toughening agent is partially crosslinked by the peroxide to reduce the permeability of the solvent to MPA6, and the MPA6 resin with better barrier property, HDPE and nano graphite micro-sheets are blended by a double screw extruder to prepare the composite material with higher barrier property.
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, 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. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The test methods used below included:
and (3) testing the permeation quantity: a film sample of HDPE/PA6 alloy is sealed on a glass bottle mouth (the diameter of the bottle mouth is 50mm) filled with 98# gasoline through silicone adhesive, the same volume of 98# gasoline is filled in the glass bottle, the glass bottle is placed in an open environment at 23-30 ℃, and the permeation amount of the 98# gasoline in glass sealed by films of different formula materials is measured after one week.
The following main reagents were used:
HDPE was used in Korean LG-DOW/PB 150.
The initiator is one or more of BIBP, DTBP, DHBP and TBPB, is a commercial product and has the same initiating effect. For example: BIBP is Acoma UPEROX F40, DTBP is Jiangsu Qiangsheng chemical industry Co., Ltd
DTBP and DHBP are of Jiangsu Qiangsheng chemical industry Co., Ltd
101 TBPB is of Jiangsu Qiangsheng chemical industry Co., Ltd
TBPH, and the like.
Example 1
Preparing the high-barrier composite material, namely firstly preparing MPA resin, wherein the dosage of the raw materials for preparing the MPA resin is as follows: 71 parts of PA6 resin, 28 parts of toughening agent, 0.5 part of initiator and 0.5 part of antioxidant. The method comprises the following specific steps:
a) weighing the raw materials according to the weight parts, premixing the dried PA6 resin, the toughening agent and the initiator in a low-speed mixer for 3-5 min, adding the antioxidant, and continuously stirring for 5-10 min;
b) placing the stirred mixture in a feeding section of a double-screw extruder, and extruding, bracing and dicing the material from a die head after the material is melted and blended by the double-screw extruder through a first section to a ninth section of the double-screw extruder; wherein the temperatures of the first section to the ninth section of the double-screw extruder are as follows in sequence: 180 to 200 ℃, 190 to 210 ℃, 200 to 230 ℃, 210 to 240 ℃, 220 to 250 ℃, 230 to 260 ℃; the die head temperature of the double-screw extruder is 230-270 ℃; the rotating speed of the double-screw machine host is 300-500 r/min; the feeding frequency is 8-20 Hz.
The MPA resin prepared by the steps is granular, the material is used for further preparing the high-barrier composite material, the dosage of each raw material is shown in table 1, and the specific steps are as follows:
c) premixing the MPA particles prepared in the step a and the step b, HDPE, compatilizer and coupling agent in a high-speed mixer for 3-5 min, adding the nano graphite micro-sheets and antioxidant, and continuously stirring for 5-10 min; placing the stirred mixture in a feeding section of a double-screw extruder, and extruding, bracing and dicing the material from a die head after the material is melted and blended by the double-screw extruder through a first section to a ninth section of the double-screw extruder; wherein the temperatures of the first section to the ninth section of the double-screw extruder are as follows in sequence: 120 to 150 ℃, 130 to 170 ℃, 140 to 190 ℃, 150 to 200 ℃, 160 to 210 ℃, 170 to 220 ℃, 180 to 230 ℃ and 180 to 240 ℃; the die head temperature of the double-screw extruder is 220-250 ℃; the rotating speed of the main machine of the double-screw machine is 300-500 r/min; feeding frequency is 8-20 Hz, and the high-barrier composite material is obtained.
d) Drying the high-barrier composite material prepared in the step (c) in a blast oven at 100 ℃ for 3 hours, injection-molding a 1 x 90 x 50mm slice by using an injection molding machine, drying for a certain time and keeping constant weight-W0, then immersing in a solvent (gasoline, cyclohexane, MMA, ethanol and water), and measuring the weight Wi at the time ti. The amount q of the blend adsorbed to the solvent was calculated from the change in mass before and after soaking. The calculation formula is as follows: q-Wi-W0, and the absorbance q/W0 results are shown in table 2.
e) And (c) drying the high-barrier composite material prepared in the step (c) in a blast oven at 100 ℃ for 3 hours, preheating a mold (the mold cavity size is 80 x 0.4mm) coated with PTFE (polytetrafluoroethylene) for 1 hour by a mold press, wherein the temperature of the mold press is 180 x 0.4mm, putting 10g of composite material particles after the mold is preheated, adjusting the mold press to enable an upper mold of the mold press to just contact the upper side of the mold, heating until the particles are completely melted, and slowly pressing down the upper mold to the specified pressure for 5 times. Cooling, opening the mold and taking out the prepared composite material film.
TABLE 1 dosage of raw materials/part by weight
Examples 2 to 10
The amounts of the respective raw materials are shown in Table 1, and the preparation method is the same as that of example 1.
Performance detection
The invention uses the adsorption quantity of the composite material to the solvent and the permeation quantity of the solvent in a certain period of time to represent the performance of the polymer for obstructing the permeation of the solvent. The smaller the adsorption amount and the smaller the permeation amount, the better the barrier property of the composite material to the solvent.
1. Table 2 shows the measured absorbance of different solvents after 36 hours when the sheets further made of the high barrier composite were immersed in water and other solvents at 60 c. It can be seen that: the water absorption of the high-barrier composite material is closely related to the MPA6 content, and the water absorption of the high-barrier composite material is increased along with the increase of the using amount of MPA 6. When the MPA6 content reached 35 parts, the water absorption was 0.42%, which is one fifth of that of pure PA 6. The water absorption resistance of the high-barrier composite material is better than that of pure PA 6. The absorption rate of the high-barrier composite material to polar solvent ethanol also conforms to the same regularity. High barrier composites are resistant to non-polar solvents such as: the absorption rates of gasoline, cyclohexane and MMA, which is a weakly polar solvent, are significantly reduced compared with pure HDPE. When the MPA6 content was 35 parts, the absorption of the high barrier composite was only one third of that of pure HDPE. The blending alloy of the kind has good performance of resisting non-polar solvent and improved water resistance.
TABLE 2 absorption rate measurement results table/wt%
| Solvent(s) | Gasoline (gasoline) | Cyclohexane | MMA | Ethanol | Water (W) |
| Example 1 | 6.1623 | 6.2865 | 2.1294 | 0.2103 | 0.2141 |
| Example 2 | 5.9148 | 6.6398 | 2.4750 | 0.4099 | 0.2253 |
| Example 3 | 5.2343 | 6.1245 | 2.1453 | 0.3882 | 0.2143 |
| Example 4 | 3.7138 | 4.8470 | 1.3135 | 0.4928 | 0.2344 |
| Example 5 | 2.0044 | 2.0108 | 0.8578 | 0.9240 | 0.4200 |
| Example 6 | 0.3326 | 2.2015 | 0.3667 | 3.2436 | 2.3565 |
The samples prepared in examples 7-10 were tested in gasoline as a solvent and all had less than 1% absorption of gasoline after 36 hours.
2. The high barrier composites prepared in examples 7-10 were subjected to the permeation test according to the film prepared in step e), as shown in the table below.
TABLE 3 results of gasoline permeation of composite materials of Experimental examples 7-10
| Examples of the experiments | Experimental example 7 | Experimental example 8 | Experimental example 9 | Experimental example 10 |
| Output (g) | 0.892 | 2.042 | 1.235 | 1.326 |
As can be seen from table 3, the gasoline permeation amount decreases with the increase of the nano-graphite micro-flake content in the composite material; the gasoline emissions decreased with increasing levels of MPA6 in the composite. The experimental data show that MPA6 and the nano graphite micro-sheet have good barrier property to gasoline.
3. The high barrier composite was injection molded into bars using an SZ-68/40 type injection machine, and the Izod impact strength was measured according to ASTM D256, the results of which are shown in Table 4.
Table 4 table of strength test results
| Group of | Impact Strength (J/m) |
| Example 1 | 175 |
| Example 2 | 221 |
| Example 3 | 251 |
| Example 4 | 273 |
| Example 5 | 321 |
| Example 6 | 639 |
| Example 7 | 183 |
| Example 8 | 341 |
| Example 9 | 243 |
| Example 10 | 192 |
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A high barrier composite characterized by: the fertilizer is prepared from the following raw materials in parts by weight: 20-99 parts of HDPE resin, 40-60 parts of MPA resin, 0.1-20 parts of compatilizer, 0.1-15 parts of nano graphite micro-sheet, 0.05-5 parts of silane coupling agent and 0.2-1.0 part of antioxidant, wherein the MPA resin is prepared from the following raw materials in parts by weight by adopting a melt extrusion process: 59-99 parts of PA6 resin, 0.1-40 parts of toughening agent, 0.2-1.0 part of initiator and 0.2-1.0 part of antioxidant.
2. The high barrier composite of claim 1, wherein: the high-barrier composite material is prepared from the following raw materials in parts by weight: 50-80 parts of HDPE resin, 40-60 parts of MPA resin, 10-20 parts of compatilizer, 3-15 parts of nano graphite micro-sheet, 1-4 parts of silane coupling agent and 0.2-1.0 part of antioxidant.
3. The high barrier composite of claim 1, wherein: the HDPE resin has a melt index of 0.01-0.05g/10min, a Shore hardness of 65-79D and the compatilizer is one or more of HDPE-MAH, HDPE-GMA, POE-MAH and POE-MAH;
optionally, the antioxidant is selected from one or more of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] tetraethoester and tri (2, 4-di-tert-butylphenol) phosphite;
optionally, the nano graphite micro-sheet has a size of 3-6um and a thickness of<15nm, specific surface area of 40-60m 2 /g。
4. The high barrier composite of claim 1, wherein: the MPA resin is prepared from the following raw materials in parts by weight by adopting a melt co-extrusion process: 60-80 parts of PA6 resin, 10-30 parts of toughening agent, 0.2-1.0 part of initiator and 0.2-1.0 part of antioxidant;
optionally, the PA6 resin has a melting point of 220-230 ℃, a relative viscosity of 2.0-2.7 and a specific gravity of 1.13-1.14g/cm 3 。
5. The high barrier composite of claim 4, wherein: the toughening agent is one or more of EPDM, EMA and EMAA;
optionally, the initiator is an organic peroxide, preferably one or more of BIBP, DTBP, DHBP and TBPB.
6. The high barrier composite of any one of claims 1-5, wherein: the absorption rate of the high-barrier composite material to gasoline after being soaked in gasoline for 36 hours is lower than 1 wt%.
7. A method for preparing the high-barrier composite material of any one of claims 1 to 6, wherein the method comprises the following steps: the method comprises the following steps:
a) weighing raw materials according to the weight parts, premixing the PA6 resin, the toughening agent and the initiator in a mixer, adding the antioxidant, and continuously stirring to obtain a mixture;
b) placing the mixture in a double-screw extruder, and performing melt blending, extrusion and grain cutting to obtain MPA resin;
c) adding the MPA resin, the HDPE resin, the compatilizer and the coupling agent into a high-speed mixer for premixing, adding the nano graphite micro-sheets and the antioxidant, and continuing stirring to obtain a resin mixture;
d) and (3) placing the resin mixture in a double-screw extruder, and performing melt blending, extrusion and granulation to obtain the high-barrier composite material.
8. The method for preparing the high-barrier composite material according to claim 7, wherein: in the step a), the dried PA6 resin, the toughening agent and the initiator are premixed in a low-speed mixer for 3-5 min, and then the antioxidant is added to continue stirring for 5-10 min to obtain a mixture;
in the step b), the mixture is placed in a feeding section of a double-screw extruder, and the mixture is melted and blended by the double-screw extruder through a first section to a ninth section of the double-screw extruder, and then is extruded from a die head, pulled into strips and cut into particles; wherein the temperatures of the first section to the ninth section of the double-screw extruder are as follows in sequence: 180 to 200 ℃, 190 to 210 ℃, 200 to 230 ℃, 210 to 240 ℃, 220 to 250 ℃, 230 to 260 ℃; the die head temperature of the double-screw extruder is 230-270 ℃; the rotating speed of the main machine of the double-screw machine is 300-500 r/min; feeding frequency is 8-20 Hz;
in the step c), adding the MPA resin, the HDPE resin, the compatilizer and the coupling agent into a high-speed mixer for premixing for 3-5 min, adding the nano-graphite micro-sheets and the antioxidant, and continuing stirring for 5-10 min to obtain a resin mixture;
in the step d), the resin mixture is placed in a feeding section of a double-screw extruder, and the materials are melted and blended by the double-screw extruder, extruded from a die head, pulled into strips and cut into granules after passing through a first section to a ninth section of the double-screw extruder; wherein the temperatures of the first section to the ninth section of the double-screw extruder are as follows in sequence: 120 to 150 ℃, 130 to 170 ℃, 140 to 190 ℃, 150 to 200 ℃, 160 to 210 ℃, 170 to 220 ℃, 180 to 230 ℃ and 180 to 240 ℃; the die head temperature of the double-screw extruder is 220-250 ℃; the rotating speed of the main machine of the double-screw machine is 300-500 r/min; the feeding frequency is 8-20 Hz.
9. A film material or a sheet material, which is prepared by drying and injection molding or blow molding the high-barrier composite material prepared by the method of any one of claims 1 to 6 or the high-barrier composite material prepared by the method of claim 7 or 8, and is characterized in that: the film material or sheet material has an absorption of less than 1 wt% in gasoline after being soaked in gasoline for 36 hours.
10. Use of the high-barrier composite material according to any one of claims 1 to 6 in packaging materials, fuel tanks for automobiles, oil pipelines.
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