CN114075356B - Polyethylene foam material with gradient pore structure and preparation method and application thereof - Google Patents
Polyethylene foam material with gradient pore structure and preparation method and application thereof Download PDFInfo
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- CN114075356B CN114075356B CN202010845499.1A CN202010845499A CN114075356B CN 114075356 B CN114075356 B CN 114075356B CN 202010845499 A CN202010845499 A CN 202010845499A CN 114075356 B CN114075356 B CN 114075356B
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- polyethylene
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- polyolefin
- antioxidant
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- -1 Polyethylene Polymers 0.000 title claims abstract description 113
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 106
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 106
- 239000006261 foam material Substances 0.000 title claims abstract description 55
- 239000011148 porous material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000005187 foaming Methods 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000004088 foaming agent Substances 0.000 claims abstract description 39
- 238000001816 cooling Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229920000098 polyolefin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000006260 foam Substances 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 46
- 229920013716 polyethylene resin Polymers 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- 238000001175 rotational moulding Methods 0.000 claims description 9
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000004156 Azodicarbonamide Substances 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 6
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000010008 shearing Methods 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000007306 functionalization reaction Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000012778 molding material Substances 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 4
- 210000000497 foam cell Anatomy 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to the technical field of foaming materials, in particular to a polyethylene foaming material with a gradient pore structure, and a preparation method and application thereof. The pore diameter of the cells of the material is 200-1500 mu m, and the pore diameter of the cells has a gradient pore structure; wherein the material is prepared by foaming a polyethylene composition, and the polyethylene composition comprises: the foaming agent comprises a matrix resin, a foaming agent and a co-foaming agent, wherein the matrix resin comprises polyolefin, a cross-linking agent, an antioxidant and a lubricant, and the shear viscosity of the matrix resin at 0.01Hz is 2500-8500 Pa.s. The polyethylene foam material provided by the invention has stronger mechanical properties, and the functionalization of the polyethylene foam material is realized; meanwhile, the foam material with the foam holes in step distribution is obtained by regulating and controlling the shearing viscosity of the matrix resin and carrying out single-side cooling foaming on the molding material, so that the controllability of molding processing is effectively improved.
Description
Technical Field
The invention relates to the technical field of foaming materials, in particular to a polyethylene foaming material with a gradient pore structure, and a preparation method and application thereof.
Background
The high molecular foaming material has light weight, strong impact load absorption capacity and heat and sound insulation capacity, and is widely applied to the fields of automobiles, buildings, packaging, catering and the like. At present, more foaming materials are used, such as polyvinyl chloride, polystyrene, polyethylene, polyurethane and the like, but the problems of high temperature difference resistance, low mechanical strength, environmental protection and difficult recovery exist more or less.
At present, the preparation method of the polymer foaming material mainly focuses on the following concentrations: the method has the respective defects of a layer-by-layer lamination method, a foaming agent content gradient control method, a foaming temperature gradient control method and a pore-foaming agent gradient distribution method, such as the problem of a lamination interface of the layer-by-layer lamination method, the severe conditions of the foaming agent content gradient control method and the foaming temperature gradient control method, and the problem of pore-foaming agent residue of the pore-foaming agent gradient distribution method.
CN107312245a discloses a gradient foaming polypropylene sheet and a preparation method thereof, wherein ultraviolet light attenuation agent is added to gradually reduce the intensity of ultraviolet light from outside to inside, so that the crosslinking degree of polypropylene is changed in a gradient manner, and the gradient change of the pore diameter of cells is caused. CN104893110a discloses a light wear-resistant density gradient sole material and a preparation method thereof, wherein the foaming material with a gradient structure is prepared mainly by controlling the foaming multiplying power, namely the density difference value of each layer of material, and adopting one-time compression molding foaming molding. CN108164831a discloses a polypropylene foam material with gradient cell structure and a preparation method thereof, mainly comprising the steps of preparing polypropylene resins with different compositions, respectively molding into sheets, then overlapping and melting, and then foaming the multilayer sheet to obtain the gradient structure.
CN104893110a and CN108164831a are both prepared into materials with certain gradient change, and then foam molding is performed, so that the method has high requirements on raw materials and complex preparation procedures; CN107312245a uses the difference of the absorption of the cross-linking agent to the ultraviolet ray to cause the melt strength of the material to change in gradient, and the method has high requirements on raw materials and technological processes.
CN109265793a discloses a low-density polyethylene foam material and a preparation method thereof, the method comprises: adding the low-density polyethylene and the SEBS modified material into an extruder, injecting butane, extruding and foaming to obtain the low-density polyethylene foaming material, wherein the extruder is a single-screw extruder which is divided into an extrusion mixing section and a cooling section.
Therefore, a new polyethylene foam material with a gradient pore structure and a preparation method thereof are needed.
Disclosure of Invention
The invention aims to solve the problems of single pore structure, lower mechanical property, high requirements on raw materials and equipment, complex operation and the like in the preparation process of the conventional polyethylene foam material.
In order to achieve the above object, a first aspect of the present invention provides a polyethylene foam material having a gradient pore structure, the material having a cell pore diameter of 200 to 1500 μm and the cell pore diameter having a gradient pore structure;
wherein the material is prepared by foaming a polyethylene composition, and the polyethylene composition comprises: matrix resin, foaming agent and auxiliary foaming agent, wherein the matrix resin comprises polyolefin, cross-linking agent, antioxidant and lubricant;
wherein the shear viscosity of the matrix resin at 0.01Hz is 2500-8500 Pa.s.
The second aspect of the present invention provides a method for preparing a polyethylene foam material having a gradient pore structure, the method comprising the steps of:
(1) Mixing polyolefin, a cross-linking agent, an antioxidant, a lubricant, a foaming agent and a auxiliary foaming agent to obtain a polyethylene composition;
(2) Granulating and grinding the polyethylene composition to obtain polyethylene resin powder;
(3) And foaming the polyethylene resin powder and cooling the polyethylene resin powder on one side to obtain the polyethylene foam material.
The third aspect of the invention provides a polyethylene foam material with a gradient pore structure prepared by the method.
The fourth aspect of the invention provides an application of the polyethylene foam material with the gradient pore structure in military packaging and heat-insulating products.
Compared with the prior art, the invention has the following advantages:
(1) The polyethylene foam material with the gradient pore structure has strong mechanical properties, achieves the functionalization of the polyethylene foam material, and widens the application of the polyethylene foam material in multiple fields;
(2) The preparation method of the polyethylene foam material with the gradient pore structure is simple, does not need multi-layer combination, simplifies the process flow and reduces the equipment requirement;
(3) According to the invention, the viscosity and the processing condition of the raw materials are doubly regulated, and particularly, the shearing viscosity of the matrix resin is regulated, and the molding material is subjected to single-side cooling foaming, so that the foam material with the foam cells distributed in steps is obtained, and the controllability of molding processing is effectively improved.
Drawings
FIG. 1 is an SEM image of a cross section of a polyethylene foam S1 prepared in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass the range or value in close proximity to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a polyethylene foam material with a gradient pore structure, wherein the pore diameter of a foam hole of the material is 200-1500 mu m, and the pore diameter of the foam hole has the gradient pore structure;
wherein the material is prepared by foaming a polyethylene composition, and the polyethylene composition comprises: matrix resin, foaming agent and auxiliary foaming agent, wherein the matrix resin comprises polyolefin, cross-linking agent, antioxidant and lubricant;
wherein the shear viscosity of the matrix resin at 0.01Hz is 2500-8500 Pa.s.
According to the invention, preferably, the gradient pore structure means that in the cross section of the material, the cell pore size gradually decreases or increases from one side to the other.
In some embodiments of the invention, as shown in fig. 1, the cell pore size gradually decreases or increases from side to side in the cross section of the polyethylene foam.
In a preferred embodiment, when the polyethylene foam is produced by rotomoulding, the cell size increases gradually from the outside to the inside in the cross section of the polyethylene foam.
In another preferred embodiment, when the polyethylene foam material is produced by pressureless foaming, in the cross section of the polyethylene foam material, the cell pore diameter gradually increases from the one-side cooling direction to the heat retaining direction.
According to the present invention, it is preferable that the cell size of the material is 200 to 800. Mu.m, and the average foaming density of the material is 0.1 to 0.5g/cm 3 Preferably 0.1-0.3g/cm 3 Wherein the cell pore size is measured by a microscopic measurement method and the average foaming density is measured according to GB/T1033.2-2008.
Preferably, the material has a compressive strength of 0.3 to 1.5MPa, preferably 0.5 to 1.2MPa, more preferably 0.8 to 1MPa, wherein the compressive strength is measured according to GB/T8813-2008.
According to the present invention, preferably, the weight ratio of polyolefin, crosslinking agent, antioxidant, lubricant, foaming agent and auxiliary foaming agent is 100:0-0.5:0.1-0.5:0-0.5:1-10:0.1-1; preferably 100:0-0.4:0.1-0.3:0-0.3:1-8:0.1-0.4. The preferable weight ratio is more beneficial to improving the mechanical property of the polyethylene foaming material.
According to a preferred embodiment of the present invention, the foamed polyethylene composition comprises 100 parts by weight of polyolefin, 0 to 0.5 parts by weight of crosslinking agent, 0.1 to 0.5 parts by weight of antioxidant, 0 to 0.5 parts by weight of lubricant, 1 to 10 parts by weight of foaming agent and 0.1 to 1 part by weight of auxiliary foaming agent.
According to a preferred embodiment of the present invention, the foamed polyethylene composition comprises 100 parts by weight of polyolefin, 0 to 0.4 parts by weight of crosslinking agent, 0.1 to 0.3 parts by weight of antioxidant, 0 to 0.3 parts by weight of lubricant, 1 to 8 parts by weight of foaming agent and 0.1 to 0.4 parts by weight of auxiliary foaming agent.
According to the present invention, preferably, the base resin has a shear viscosity of 3000 to 7000 Pa.s at 0.01 Hz. The preferable conditions are adopted, so that the polyethylene foam material is more favorable to have a gradient structure. Specifically, when the shear viscosity is too large, the polyethylene foam material does not foam; when the shear viscosity is too low, the cell size of the polyethylene foam is too large.
In a preferred embodiment of the present invention, a polyolefin, a crosslinking agent, an antioxidant and a lubricant are mixed in a certain weight ratio to obtain a matrix resin having a shear viscosity of 2500 to 8500 Pa.s at 0.01 Hz.
Preferably, the parameters of the polyolefin satisfy: the density is 0.91-0.96g/cm 3 Preferably 0.93-0.94g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index at 190℃and 2.16kg load is 2-30g/10min, preferably 5-10g/10min; wherein the melt index at 190℃and 2.16kg load is measured according to GB/T3682-2000.
In the present invention, the polyolefin has a wide selection range as long as the polyolefin contains polyethylene. Preferably, the polyolefin is selected from polyethylene and/or thermoplastic elastomer, preferably polyethylene.
In some embodiments of the present invention, preferably, the thermoplastic elastomer is a copolymer of ethylene and an α -olefin selected from at least one of butene, hexene and octene, for example, the thermoplastic elastomer may be an ethylene-butene copolymer and/or an ethylene-octene copolymer, but the present invention is not limited thereto.
In the present invention, in order to extrude the particles and then foam, it is preferable that the decomposition temperature of the foaming agent is 30-80 ℃ higher than the melting point temperature of the matrix resin.
In the present invention, the foaming agent is selected from the group consisting of azodicarbonamide, 4-oxo-bis-benzenesulfonyl, N-dinitroso pentamethylene tetra-ammonium, sodium bicarbonate, ammonium bicarbonate and sodium citrate.
Preferably, the crosslinking agent is at least one selected from the group consisting of dicumyl peroxide, benzoyl peroxide, 1, 3-bis (t-butylperoxyisopropyl) benzene and 2, 5-dimethyl-2, 5-bishexane.
Preferably, the co-foaming agent is selected from zinc oxide and/or zinc stearate.
Preferably, the antioxidant is selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and/or tris (2, 4-di-tert-butylphenyl) phosphite, wherein pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is abbreviated as oxidant 1010 and tris (2, 4-di-tert-butylphenyl) phosphite is abbreviated as oxidant 168.
Preferably, the lubricant is selected from calcium stearate and/or white oil.
According to the invention, the polyolefin, the cross-linking agent, the antioxidant, the lubricant, the foaming agent and the auxiliary foaming agent are mixed according to a certain weight ratio, and the shearing viscosity of matrix resin containing the polyolefin, the cross-linking agent, the antioxidant and the lubricant is limited, so that the foaming efficiency of the polyethylene foaming material is improved, and the polyethylene foaming material with a gradient pore structure is obtained.
The second aspect of the present invention provides a method for preparing a polyethylene foam material having a gradient pore structure, the method comprising:
(1) Mixing polyolefin, a cross-linking agent, an antioxidant, a lubricant, a foaming agent and a auxiliary foaming agent to obtain a polyethylene composition;
(2) Granulating and grinding the polyethylene composition to obtain polyethylene resin powder;
(3) And foaming the polyethylene resin powder and cooling the polyethylene resin powder on one side to obtain the polyethylene foam material.
In the present invention, in order to uniformly mix the polyethylene composition, it is preferable that the mixing is performed in a mix; further preferably, the mixing conditions include: the temperature is 15-40deg.C, preferably 15-30deg.C; the time is 1-30min, preferably 2-10min. With the preferred conditions, it is more advantageous to obtain a homogeneous polyethylene composition.
In the present invention, the pelletization means that the polyethylene composition is converted into polyethylene resin pellets, and preferably, the pelletization is performed in an extruder selected from a twin-screw extruder and/or a single-screw extruder. Further preferably, the conditions for granulation include: the extrusion temperature is 120-150 ℃, preferably 125-135 ℃; the screw speed is 80-150rpm, preferably 90-110rpm.
According to a preferred embodiment of the present invention, the polyethylene composition obtained in the step (1) is fed into a twin-screw extruder to be extruded and pelletized, and the polyethylene resin pellets are milled to obtain polyethylene resin powder.
In the present invention, the foaming means that the polyethylene resin powder is subjected to a mold to obtain a polyethylene foam material, and preferably the foaming is selected from rotational molding foaming and/or pressureless foaming.
In some embodiments of the invention, preferably, the foaming conditions include: the temperature is 150-250deg.C, preferably 170-210 deg.C, and the time is 10-30min, preferably 12-20min.
In some embodiments of the invention, preferably, when the foaming is rotomoulding foaming, the means of single-sided cooling is selected from single-sided air cooling and/or single-sided water cooling.
In some embodiments of the invention, preferably, when the foaming is pressureless foaming, the one-sided cooling comprises: and (3) introducing water and/or wind to one side along the thickness direction of the foam for cooling, and preserving heat at the other side, wherein the temperature difference of the two sides is more than 50 ℃.
In the invention, the polyethylene resin powder is subjected to single-side cooling foaming, and the cooling temperature is changed in a gradient manner in the cooling process by controlling the shearing viscosity of the matrix resin containing polyolefin, a cross-linking agent, an antioxidant and a lubricant, so that the pore diameter of the foam holes of the material is changed in a gradient manner, that is, the foam holes on the side with high cooling speed are smaller, the heat preservation time on the side with slower cooling is longer, and the foam holes are larger.
In the present invention, the types and amounts of the polyolefin, the crosslinking agent, the antioxidant, the lubricant, the foaming agent and the auxiliary foaming agent are defined according to the above description, and the present invention is not repeated herein.
The third aspect of the invention provides a polyethylene foam material with a gradient pore structure prepared by the method.
In the invention, the polyethylene foam material has a gradient pore structure and excellent mechanical properties, and can effectively realize the functionalization of the polyethylene foam material.
The fourth aspect of the invention provides an application of the polyethylene foam material with the gradient pore structure in military packaging and heat-insulating products.
The present invention will be described in detail by examples.
Melt index of polyethylene at 190℃and 2.16kg under load was measured according to GB/T3682-2000;
the pore diameter of the foam cells of the polyethylene foam material is measured by a microscopic measuring method;
the average foaming density of the polyethylene foaming material is measured according to GB/T1033.2-2008;
the compression strength of the polyethylene foam material is measured according to GB/T8813-2008;
compression set of the polyethylene foam material is measured according to HG/T1876-2009;
the hardness of the polyethylene foam material was measured according to GB/T531.1-2008.
The conditions for preparing the polyethylene foam materials in examples 1 to 4 and comparative examples 1 to 5 are shown in Table 1, and the performance parameters of the polyethylene foam materials prepared in examples 1 to 4 and comparative examples 1 to 5 are shown in Table 2.
Example 1
(1) Polyethylene (density 0.925 g/cm) 3 Melt index at 190 ℃ and 2.16kg load is 3.5g/10 min), dicumyl peroxide, antioxidant 1010, antioxidant 168, azodicarbonamide and zinc oxide are mixed in a mixer to obtain a polyethylene composition, wherein the mixing conditions comprise: the temperature is 25 ℃ and the time is 3min;
(2) Extruding, granulating and grinding the polyethylene composition in a double-screw extruder to obtain polyethylene resin powder, wherein the double-screw extruding, granulating conditions comprise: the extrusion temperature was 125℃and the screw speed was 100rpm; granulating, drying at 60deg.C for 2 hr, and grinding to obtain granule;
(3) And (3) performing rotational molding foaming on the polyethylene resin powder, and cooling the polyethylene resin powder with air at one side for 25min after the foaming of the material is completed to obtain a polyethylene foam material S1, wherein the rotational molding foaming conditions comprise: the temperature was 220℃and the time was 18min.
As shown in fig. 1, the microscopic photograph of the polyethylene foam material S1 shows that the polyethylene foam material has a gradient pore structure, i.e., in the cross section of the polyethylene foam material S1, the pore size of the cells gradually increases from outside to inside, wherein the outer refers to the bottom of fig. 1, and the inner refers to the top of fig. 1.
Example 2
(1) Polyethylene (density 0.945 g/cm) 3 Melt index at 190℃and 2.16kg of load is 4.1g/10 min), benzoyl peroxide, antioxidant 1010, antioxidant 168, azodicarbonamide and zinc stearate in a mixer to obtain a polyethylene composition, wherein the mixing conditions include: the temperature is 25 ℃ and the time is 3min;
(2) Extruding, granulating and grinding the polyethylene composition in a double-screw extruder to obtain polyethylene resin powder, wherein the double-screw extruding, granulating conditions comprise: the extrusion temperature was 120℃and the screw speed was 100rpm; granulating, drying at 60deg.C for 2 hr, and grinding to obtain granule;
(3) And (3) performing rotational molding foaming on the polyethylene resin powder, and cooling the polyethylene resin powder with air at one side for 25min after the foaming of the material is completed to obtain a polyethylene foaming material S2, wherein the rotational molding foaming conditions comprise: the temperature was 220℃and the time was 18min.
Wherein, the SEM image of the polyethylene foam S2 is similar to FIG. 1.
Example 3
(1) POE (ethylene-butene copolymer, density of 0.915 g/cm) 3 Melt index at 190℃and 2.16kg load of 2.5g/10 min), polyethylene (density 0.945g/cm 3 Melt index at 190 ℃ and under a load of 2.16kg is 4.1g/10 min), antioxidant 1010, azodicarbonamide and zinc stearate are mixed in a mixer to obtain a polyethylene composition, wherein the weight ratio of POE to polyethylene is 3:7, and the mixing conditions comprise: the temperature is 30 ℃ and the time is 3min;
(2) Extruding, granulating and grinding the polyethylene composition in a double-screw extruder to obtain polyethylene resin powder, wherein the double-screw extruding, granulating conditions comprise: the extrusion temperature was 125℃and the screw speed was 100rpm; granulating, drying at 60deg.C for 2 hr, and grinding to obtain granule;
(3) Carrying out pressureless foaming on the polyethylene resin powder, and after the foaming of the material is completed, carrying out unilateral cooling along the thickness direction of the foaming, wherein unilateral cooling comprises that one side is filled with water for cooling, the other side is insulated, the temperature difference of the two sides is 60 ℃, and the polyethylene foaming material S3 is obtained, wherein the pressureless foaming conditions comprise: the temperature was 200℃and the time was 10min.
Wherein the pore diameter of the foam cells of the polyethylene foam material S3 is gradually increased from the one-side cooling direction to the heat preservation direction, and the SEM image of the polyethylene foam material S3 is similar to that of FIG. 1.
Example 4
The procedure of example 1 was followed except that white oil was added in step (1) to obtain a polyethylene foam S4.
Comparative example 1
According to the method of example 1, except that 12 parts by weight of azodicarbonamide was replaced, a polyethylene foam material D1 was obtained, wherein cells of the polyethylene foam material D1 were melted and integrated to obtain a foam material, and the mechanical property test was not performed.
Comparative example 2
The procedure of example 1 was followed except that the weight ratio of polyethylene, dicumyl peroxide, antioxidant 1010 and antioxidant 168 was adjusted so that the base resin had a shear viscosity of 9000 Pa.s at 0.01Hz, to obtain a polyethylene foam D2.
Comparative example 3
The procedure of example 3 was followed except that the weight ratio of polyethylene, dicumyl peroxide, antioxidant 1010 and antioxidant 168 was adjusted so that the shear viscosity of the matrix resin at 0.01Hz was 2000 Pa.s, to obtain a polyethylene foam D3.
Comparative example 4
The procedure of example 2 was followed except that the weight ratio of polyethylene, benzoyl peroxide, antioxidant 1010 and antioxidant 168 was adjusted so that the base resin had a shear viscosity of 12000 Pa.s at 0.01Hz, to obtain a polyethylene foam D4.
Comparative example 5
The procedure of example 1 was followed except that the one-sided air cooling in step (3) was replaced with two-sided air cooling to obtain a polyethylene foam material D5.
TABLE 1
Note that: * -a shear viscosity at 0.01Hz of a matrix resin comprising polyolefin, cross-linker, antioxidant and lubricant;
* Polyolefin: crosslinking agent: an antioxidant: and (3) a lubricant: the weight ratio of the foaming agent to the auxiliary foaming agent.
As can be seen from the data in Table 1, examples 1 to 4 produced polyethylene foam materials having a gradient cell structure by defining a foaming mode of a matrix resin (0.01 Hz shear viscosity of 2500 to 8500 Pa.s) and one-side cooling, as compared with comparative examples 1 to 5. Therefore, the pore diameter of the foam cells of the polyethylene foam material prepared by the method provided by the invention has a gradient structure.
TABLE 2
As can be seen from the data in Table 2, the polyethylene foam material prepared by the method provided by the invention has higher mechanical properties, namely, the polyethylene foam material provided by the invention has higher compressive strength and tensile strength, lower compression set and thermal conductivity through comparing example 1 with comparative examples 2 and 5, example 2 with comparative example 4 and example 3 with comparative example 3, and can be widely applied to military packaging and thermal insulation products.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (25)
1. A polyethylene foam material with a gradient pore structure, which is characterized in that the pore diameter of a foam hole of the material is 200-1500 mu m, and the pore diameter of the foam hole has a gradient pore structure;
wherein the material is prepared by the following method: (1) Mixing matrix resin, a foaming agent and a foaming aid to obtain a polyethylene composition; the matrix resin comprises polyolefin, a cross-linking agent, an antioxidant and a lubricant; (2) Granulating and grinding the polyethylene composition to obtain polyethylene resin powder; (3) Foaming and cooling the polyethylene resin powder on one side to obtain the material; wherein the foaming is selected from rotational moulding foaming and/or pressureless foaming;
wherein the shear viscosity of the matrix resin at 0.01Hz is 2500-8500 Pa.s;
wherein the weight ratio of polyolefin, cross-linking agent, antioxidant, lubricant, foaming agent and auxiliary foaming agent is 100:0-0.5:0.1-0.5:0-0.5:1-10:0.1-1;
wherein the decomposition temperature of the foaming agent is 30-80 ℃ higher than the melting point temperature of the matrix resin, and the foaming agent is at least one selected from azodicarbonamide, 4-oxo-bis-benzenesulfonyl hydrazide, N-dinitroso pentamethylene tetra-ammonium, sodium bicarbonate, ammonium bicarbonate and sodium citrate.
2. The material of claim 1, wherein the gradient pore structure means that in a cross section of the material, the cell pore size gradually decreases or increases from side to side.
3. The material of claim 2, wherein the material has an average foam density of 0.1-0.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The compressive strength of the material is 0.3-1.5MPa.
4. The material of claim 2, wherein the material has an average foam density of 0.1-0.3g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The compressive strength of the material is 0.5-1.2MPa.
5. The material of claim 1, wherein the polyolefin, crosslinking agent, antioxidant, lubricant, blowing agent, and co-blowing agent are present in a weight ratio of 100:0-0.4:0.1-0.3:0-0.3:1-8:0.1-0.4.
6. The material of any of claims 1-5, wherein the matrix resin has a shear viscosity of 3000-7000 Pa-s at 0.01 Hz.
7. The material of claim 6, wherein the polyolefin has parameters that satisfy: the density is 0.91-0.96g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index at 190 ℃ and under a load of 2.16kg is 2-30g/10min.
8. The material of claim 6, wherein the polyolefin has parameters that satisfy: the density is 0.93-0.94g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index at 190℃and 2.16kg load is 5-10g/10min.
9. The material of claim 6, wherein the polyolefin is selected from polyethylene and/or thermoplastic elastomers.
10. The material of claim 6, wherein the polyolefin is polyethylene.
11. The material of claim 9, wherein the thermoplastic elastomer is a copolymer of ethylene and an alpha-olefin selected from at least one of butene, hexene, and octene.
12. The material according to any one of claims 1 to 5, wherein,
the auxiliary foaming agent is selected from zinc oxide and/or zinc stearate.
13. The material of claim 12, wherein the cross-linking agent is selected from at least one of dicumyl peroxide, benzoyl peroxide, 1, 3-bis (t-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-bishexane.
14. The material of claim 12, wherein the antioxidant is selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or tris (2, 4-di-tert-butylphenyl) phosphite.
15. The material of claim 12, wherein the lubricant is selected from calcium stearate and/or white oil.
16. A method for producing a polyethylene foam material having a gradient cell structure as claimed in any one of claims 1 to 15, characterized in that the method comprises the steps of:
(1) Mixing polyolefin, a cross-linking agent, an antioxidant, a lubricant, a foaming agent and a auxiliary foaming agent to obtain a polyethylene composition;
(2) Granulating and grinding the polyethylene composition to obtain polyethylene resin powder;
(3) And foaming the polyethylene resin powder and cooling the polyethylene resin powder on one side to obtain the polyethylene foam material.
17. The method of claim 16, wherein the mixing conditions comprise: the temperature is 15-40 ℃; the time is 1-30min.
18. The method of claim 17, wherein the mixing conditions comprise: the temperature is 15-30 ℃; the time is 2-10min.
19. The method of claim 17, wherein the granulating conditions comprise: the extrusion temperature is 120-150 ℃; the screw speed was 80-150rpm.
20. The method of claim 17, wherein the granulating conditions comprise: the extrusion temperature is 125-135 ℃; the screw speed was 90-110rpm.
21. The method of any of claims 16-20, wherein the foaming conditions comprise: the temperature is 150-250deg.C, and the time is 10-30min.
22. The method of claim 21, wherein the foaming conditions comprise: the temperature is 170-210 ℃ and the time is 12-20min.
23. The method of claim 21, wherein when the foaming is rotomoulding foaming, the one-sided cooling is selected from one-sided air cooling and/or one-sided water cooling.
24. The method of claim 21, wherein when the foaming is pressureless foaming, the single-sided cooling comprises: and (3) introducing water and/or wind to one side along the thickness direction of the foam for cooling, and preserving heat at the other side, wherein the temperature difference of the two sides is more than 50 ℃.
25. Use of a polyethylene foam material having a gradient pore structure as claimed in any one of claims 1 to 15 in military packaging and insulation products.
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