CN112759813A - Crosslinked polyolefin foamed sheet and preparation method thereof - Google Patents
Crosslinked polyolefin foamed sheet and preparation method thereof Download PDFInfo
- Publication number
- CN112759813A CN112759813A CN202011626110.0A CN202011626110A CN112759813A CN 112759813 A CN112759813 A CN 112759813A CN 202011626110 A CN202011626110 A CN 202011626110A CN 112759813 A CN112759813 A CN 112759813A
- Authority
- CN
- China
- Prior art keywords
- polyolefin resin
- foamed sheet
- ethylene
- polyolefin
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 77
- 238000005187 foaming Methods 0.000 claims abstract description 32
- 239000004088 foaming agent Substances 0.000 claims abstract description 30
- 238000004132 cross linking Methods 0.000 claims abstract description 22
- 238000007906 compression Methods 0.000 claims abstract description 21
- 230000006835 compression Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 229920001577 copolymer Polymers 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 20
- -1 polypropylene Polymers 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 239000004711 α-olefin Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 239000004156 Azodicarbonamide Substances 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 8
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 8
- 229920001684 low density polyethylene Polymers 0.000 claims description 8
- 239000004702 low-density polyethylene Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000004704 Ultra-low-molecular-weight polyethylene Substances 0.000 claims description 6
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 6
- 229920001903 high density polyethylene Polymers 0.000 claims description 6
- 239000004700 high-density polyethylene Substances 0.000 claims description 6
- 229920001179 medium density polyethylene Polymers 0.000 claims description 6
- 239000004701 medium-density polyethylene Substances 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 6
- 239000011118 polyvinyl acetate Substances 0.000 claims description 6
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- VRFNYSYURHAPFL-UHFFFAOYSA-N [(4-methylphenyl)sulfonylamino]urea Chemical compound CC1=CC=C(S(=O)(=O)NNC(N)=O)C=C1 VRFNYSYURHAPFL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 claims description 3
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- 238000012685 gas phase polymerization Methods 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000012968 metallocene catalyst Substances 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000002832 nitroso derivatives Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 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 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 28
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 238000010998 test method Methods 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- YYDSJSUGHIXOFC-UHFFFAOYSA-N (4,6-dihydrazinyltriazin-5-yl)hydrazine Chemical compound NNC1=NN=NC(NN)=C1NN YYDSJSUGHIXOFC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
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- 230000020169 heat generation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
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- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- 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
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- 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
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- 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
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- 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
- C08J2323/08—Copolymers of ethene
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- 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
- C08J2423/06—Polyethene
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- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a crosslinked polyolefin foamed sheet and a preparation method thereof, belonging to the field of high polymer foam, wherein the foamed sheet has the thickness of 0.01-0.5 mm and the density of 0.3g/cm3～0.8g/cm3When the compression deformation is 50%, the compression stress is less than or equal to 2MPa, when at least 60g of small balls fall from the height of more than 35mm, the foamed sheet body is not cracked, the closed cell rate is more than 85%, and the cross-linking is carried outThe density is 15-70%. When the polyolefin resin is prepared, the raw materials comprise a first type polyolefin resin, a second type polyolefin resin and a foaming agent, wherein the first type polyolefin resin is a polyolefin resin with the falling weight impact of more than or equal to 130g, and the using amount of the first type polyolefin resin is more than 8% of the mass sum of the first type polyolefin resin and the second type polyolefin resin. The invention also discloses a method for preparing the foamed sheet. The foaming sheet disclosed by the invention can meet the actual engineering requirements on strength, toughness and space following capability under the condition of relatively small thickness, and the preparation method is simple.
Description
Technical Field
The invention belongs to the field of foamed sheets, and particularly relates to a crosslinked polyolefin foamed sheet and a preparation method thereof.
Background
At present, the electronic product is thin and miniaturized and is trended obviously, and electronic product display module integrates and multi-functional demand is more and more obvious, no matter be in order to display panel, electronic components's protection, still from enlarging the high screen of electronic display equipment and occupying ratio to and the space of arranging of other devices of guarantee electronic product/equipment inside considers, and the frame is with sealed buffering bubble cotton to the requirement of tolerating the impact and the requirement of the cushion performance that can provide more and more high.
In the conventional products, the foam material generally has a low density or a high foaming ratio to ensure flexibility, and when such products for electronic use are cut into narrow frames, for example, a width of 0.7mm or less, the strength of the foam material body is low, and when the products are subjected to external force impact, the foam is likely to be broken in the thickness direction, and the protection performance is lost.
Therefore, it is necessary to develop a novel crosslinked polyolefin foamed sheet and a method for preparing the same, which can meet the practical needs.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to obtain the crosslinked polyethylene foamed sheet with specific performance by extremely fine adjustment, optimization and proportioning on the structure, the components and the formula, and meet the comprehensive requirements of practical engineering on the toughness and the space following capability of the foamed sheet under the condition of thinner thickness.
In order to achieve the aim, the invention provides a crosslinked polyolefin foamed sheet, the thickness of the foamed sheet is 0.01-0.5 mm, and the density is 0.3g/cm3～0.8g/cm3When the compression deformation is 50%, the compression stress is less than or equal to 2MPa, when at least 60g of small balls fall from the height of more than 35mm, the foamed sheet body is not broken, and the closed cell ratio is 85% or more, and the crosslinking degree is 15-70%.
Further, during preparation, the raw materials comprise a first type polyolefin resin, a second type polyolefin resin and a foaming agent, wherein the first type polyolefin resin is a polyolefin resin with the falling weight impact of more than or equal to 130g, the using amount of the first type polyolefin resin is more than 8% of the sum of the mass of the first type polyolefin resin and the mass of the second type polyolefin resin, and the first type polyolefin resin and the second type polyolefin resin have different properties.
Further, the first type of polyolefin resin comprises vinyl resin copolymerized by alpha olefin monomer and ethylene monomer with 3-8 carbon atoms, and is prepared by gas phase polymerization or solution polymerization by adopting a Ziegler-Natta catalyst, a metallocene catalyst and a bifunctional catalyst or a catalyst containing aluminum, zirconium, iron, titanium, manganese, chromium, nickel, palladium or/and platinum metal elements, wherein the mass of the alpha olefin monomer is less than 30% of the total mass of all the monomers.
Further, the vinyl resin is one or more of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer and ethylene-octene copolymer.
Further, the second polyolefin resin is one or more of polypropylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, metallocene polyethylene, low-molecular-weight polyethylene, ultra-low-molecular-weight polyethylene, polyethylene wax, ethylene-propylene binary copolymer, ethylene-propylene ternary copolymer, ethylene-vinyl acetate copolymer, polyvinyl acetate, ethylene-acrylic acid copolymer and ethylene-acrylic ester copolymer.
Further, the melting point of the first polyolefin resin is 70-140 ℃, the melt index is 0.2-6.2 g/10min under the conditions of 2.16Kg load and 190 ℃, and the density is 0.840-0.940 g/cm3。
Furthermore, the melting point of the second polyolefin resin is 60-165 ℃, the melt index of the second polyolefin resin is 0.1-7.0 g/10min under 2.16Kg load and 190 ℃, and the difference of the melt index of the second polyolefin resin and the melt index of the first polyolefin resin under the same condition is not more than 5.0.
Further, when prepared, the foaming agent comprises a physical foaming agent and a chemical foaming agent, wherein the physical foaming agent comprises one or more of nitrogen, carbon dioxide, butane or expanded microspheres, when the physical foaming agent is used, the foaming is performed by adopting an extrusion or die-pressing foaming process, and the chemical foaming agent comprises one or more of azodicarbonamide, 2 ' -azodiisobutyronitrile, diisopropyl azodicarboxylate, barium azodicarboxylate, diethyl azodicarboxylate, azoaminobenzene, nitroso compound, N ' -dimethyl-N, N ' -dinitrosoterephthalamide, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, p-toluenesulfonylsemicarbazide, 5-phenyltetrazole, trihydrazinyltriazine, sodium bicarbonate, sodium carbonate, citric acid, sodium citrate and hydrates thereof.
Further, during preparation, the particle size of azodicarbonamide is 2-50 μm, and the distribution Span is 1.0-2.0.
According to the second aspect of the present invention, there is also provided a method of crosslinking a polyolefin foamed sheet, comprising the steps of:
s1: preparing different master batches, wherein the master batches comprise a foaming agent, resin, toner and an auxiliary agent, the resin comprises a first polyolefin resin and a second polyolefin resin, the first polyolefin resin is a polyolefin resin with the falling weight impact of more than or equal to 130g, the using amount of the first polyolefin resin is more than 8 percent of the mass sum of the first polyolefin resin and the second polyolefin resin,
the second polyolefin-based resin comprises one or more of the following: polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, metallocene polyethylene, low molecular weight polyethylene, ultra-low molecular weight polyethylene, polyethylene wax, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-propylene terpolymers, polyvinyl acetate, ethylene-acrylic acid copolymers, and ethylene-acrylic acid ester copolymers,
s2: mixing different master batches in advance, melting and extruding the mixture into sheets at the temperature of between 90 and 125 ℃,
s3: the sheet material in the step S2 is processed by high-energy electron irradiation crosslinking treatment, the crosslinking degree of the sheet material is 10-60 percent,
s4: the crosslinked sheet in the step S3 is subjected to foaming process treatment at a temperature of 185-300 ℃,
s5: and (4) heating the foamed sheet obtained in the step (S4), and performing stretching orientation and thinning treatment to obtain a crosslinked polyolefin foamed sheet.
Through the technical scheme, compared with the prior art, the invention can obtain the following beneficial effects:
in the invention, in order to prepare the foamed sheet with the density, the strength, the toughness and the gap following capability which simultaneously meet the requirements, the foamed sheet is finely designed and matched according to the detailed parameters of components, the performance requirements of the components, the proportion, the process parameters and the like, and the foamed sheet with the comprehensive performance of the density, the strength, the toughness and the gap following capability which can meet the novel requirements is prepared and can be suitable for the frame sealing material of electronic products.
Drawings
FIG. 1 is a flow chart of a method of making a foamed sheet of the present invention;
FIG. 2 is a schematic structural diagram for testing the overall performance of the foamed sheet of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a foamed sheet having cushioning properties and impact resistance even when the foamed sheet is thinned. The invention creatively uses the vinyl resin (namely the first type of polyolefin resin) with the falling weight impact exceeding a certain limit value in the formula, adjusts the apparent density to a specific range, and obtains the foamed sheet capable of meeting the actual engineering requirements by matching with the improvement on the structure.
The foamed sheet of the invention has the thickness of 0.01 mm-0.5 mm and the density of 0.3g/cm3～0.8g/cm3When the compression deformation is 50%, the compression stress is less than or equal to 2MPa, and at least 60g of small ballsThe foamed sheet body is not broken when falling from the height of at least 35mm, the closed cell rate is more than 85 percent, and the crosslinking degree is 10 to 70 percent. The foamed sheet with the performances has the performances of toughness, gap adaptability, light weight and high strength, and can be used for frame sealing and vibration damping foam of electronic functional equipment.
FIG. 1 is a flow chart of a method for preparing a foamed sheet of the present invention, and it can be seen that the method for preparing a foamed sheet of crosslinked polyolefin as described above specifically comprises the following steps:
s1: preparing different master batches, wherein the master batches comprise foaming agents, resins, toner and auxiliaries, the resins comprise first polyolefin resins and second polyolefin resins, the first polyolefin resins are polyolefin resins with the falling weight impact of more than or equal to 130g, the using amount of the first polyolefin resins is more than 8% of the mass sum of the first polyolefin resins and the second polyolefin resins, and the second polyolefin resins comprise one or more of the following components: polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, metallocene polyethylene, low molecular weight polyethylene, ultra-low molecular weight polyethylene, polyethylene wax, ethylene-propylene copolymers, ethylene-propylene terpolymers, polyvinyl acetate, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, and ethylene-acrylic ester copolymers. The first type of polyolefin resin comprises vinyl resin copolymerized by alpha olefin monomer and ethylene monomer with 3-8 carbon atoms, and is prepared by gas phase polymerization or solution polymerization by adopting a Ziegler-Natta catalyst, a metallocene catalyst, a bifunctional catalyst or a catalyst containing aluminum, zirconium, iron, titanium, manganese, chromium, nickel, palladium or/and platinum metal elements, wherein the mass of the alpha olefin monomer is less than 30% of that of the ethylene monomer, and preferably the mass of the alpha olefin monomer is less than 10% of that of the ethylene monomer. The melting point of the first polyolefin resin is 70-140 ℃, the melt index is 0.2-6.2 g/10min, and the density is 0.840-0.940 g/cm3。
The second type of resin comprises one or more of the following: polypropylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, metallocene polyethylene, low-molecular-weight polyethylene, ultra-low-molecular-weight polyethylene, polyethylene wax, ethylene-propylene binary copolymer, ethylene-propylene ternary copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer and ethylene-acrylate copolymer, wherein the melting point of the second resin is 60-165 ℃, the melt index of the second resin at 190 ℃ is 0.1-7.0 g/10min, and the melt index difference between the second resin and the first polyolefin resin at 190 ℃ is not more than 5.0.
S2: mixing the different master batches in advance, and melting and extruding the mixture into sheets at the temperature of between 90 and 125 ℃.
S3: and (3) subjecting the sheet in the step S2 to high-energy electron irradiation crosslinking treatment, wherein the crosslinking degree of the sheet is 10-70%, and the crosslinking degree of the sheet is preferably 20-58%.
S4: and (3) performing foaming process treatment on the crosslinked sheet in the step S3 at the temperature of 185-300 ℃.
S5: and (4) heating the foamed sheet obtained in the step (S4), and performing stretching orientation and thinning treatment to obtain a crosslinked polyolefin foamed sheet.
In the present invention, the first type of polyolefin resin having a certain dart drop strength is a vinyl resin obtained by copolymerizing a C3-C8 monomer with a vinyl monomer. The C3-C8 are copolymerized by alpha olefin monomers with 3-8 carbon atoms and ethylene. For example, the α -olefin is 30% by mass or less, preferably 10% by mass or less, of the total monomers. All monomers refer to the total mass of monomers required to synthesize the ethylene copolymer. Specific examples of the α -olefin constituting the polyethylene resin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene.
The melting point of the first type of polyolefin resin with certain dart drop strength is 70-140 ℃, the test method is DIN53765, and the melting point is preferably 80-130 ℃ and further preferably 100-127 ℃ by adopting Mettler Toledo DSC 3 test. The melting point of the resin is too high, and the difference between the melting point of the resin and the melting point of the resin is too large, so that an area which is not completely or partially melted and plasticized is easily caused, and finally, a foamed product is broken or the performance of the foamed product is damaged due to stress concentration; the melting point is low excessively, and the temperature resistance of the foaming product is poor, and in the application of electronic products, because components generate heat during working, creep deformation can be generated quickly, so that assembly gaps generate gaps, and the sealing performance is lost.
The first type of polyolefin resin with certain dart drop strength has a melt index of 0.2-6.2 g/10min, a test method of ASTM D1238, a test pressure of 2.16kg and a test temperature of 190 ℃. Preferably 0.5 to 5.4g/10min, and more preferably 0.8 to 4.5g/10 min. The melt index is too low, the fluidity is poor, excess materials are easy to be left in the extrusion stage, and finally the performance of a product is not uniform; the melt index is too high, and the difference from the fluidity of other component resins is large, so that excess materials caused by uneven extrusion flow distribution are generated, wherein low molecular weight parts are easy to precipitate at the die of an extrusion die due to shearing, and after long-time accumulation, the precipitates become large and are adhered to the surface of a sheet continuously extruded to generate apparent defects of an extruded foaming sheet.
The density of the first type of polyolefin resin with certain dart drop strength is 0.840-0.940 g/cm3Tested according to ASTM D792; the density is preferably 0.847 to 0.936, more preferably 0.860 to 0.935g/cm3. Due to too low density, when the foaming material is impacted, the impact stress dispersion capability of the foaming material surface is poor, the impact stress is too much concentrated at an impact point, and the impact stress cannot be dissipated; the high density, the high melting point of the resin and the long melting range can lead to incomplete plasticization in the granulation and extrusion stages or uneven dispersion of the materials due to inconsistent plasticization, which leads to poor uniformity of physical properties.
The first type of polyolefin resin having a certain dart drop strength will be combined with the second type of resin to constitute the matrix resin portion of the foam. The melting point of the second type resin is 60-165 ℃, and preferably 65-160 ℃; further preferably 68-156 ℃; the melting point is too low, the whole temperature resistance of the foaming material is poor, the foaming material is easy to soften due to the temperature rise caused by the heat generation of electronic products in the frame application of the electronic products, and the sealing property of the electronic product is easy to lose when the substrate temperature is higher. The melting point is too high, the resin can be melted and plasticized only by higher extrusion temperature, so that the foaming agent is easily decomposed in the extrusion process, and stress concentration points are generated, so that the performance of the foaming product is reduced. The melt index of the second resin at 190 ℃ is preferably 0.1-7.0 g/10min, and preferably 0.3-6.5 g/10 min; further preferably 0.6 to 5.8g/10 min. Wherein the difference in melt index at 190 ℃ between the second resin and the polyolefin having a dart drop strength is not more than 5.0, preferably not more than 4.2, and more preferably not more than 4.0. Too large a difference in melt index and large a difference in fluidity cause uneven kneading and uneven distribution of properties.
The used foaming agent comprises a physical foaming agent and a chemical foaming agent, wherein the physical foaming agent comprises one or two or more of nitrogen, carbon dioxide, butane or expanded microspheres; preferably nitrogen or carbon dioxide, and the foamed product is prepared by adopting an extrusion or mould pressing foaming process when a physical foaming agent is used. Chemical blowing agents include azodicarbonamide, 2 ' -azobisisobutyronitrile, diisopropyl azodicarboxylate, barium azodicarboxylate, diethyl azodicarboxylate, azoaminobenzene, nitroso compounds, N ' -dimethyl-N, N ' -dinitrosoterephthalamide, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, p-toluenesulfonylsemicarbazide, 5-phenyltetrazole, trihydrazinotriazine, sodium bicarbonate, sodium carbonate, citric acid, sodium citrate, or hydrates thereof. The physical foaming agent and the chemical foaming agent are preferably chemical foaming agents, and azodicarbonamide is preferably used as the chemical foaming agent. The particle size of azodicarbonamide is preferably 2-50 μm, and the distribution Span is 1.0-2.0; further preferably 3-48 μm, and the distribution Span is 1.0-1.7. The particle size is too small, the dispersion is difficult, and the uniformity of foam pores of a foaming product is poor; too large particle size, too high decomposition temperature, slow foaming speed, high foaming temperature, too long time of the foam matrix resin matrix in a high-temperature field of a foaming furnace, degradation and further performance reduction.
The particle size of the foaming agent is tested by using a laser particle size analyzer, the particle size is tested by adopting a Bettersize 2600 device in Dandong, and D50 data is used as a particle size test result; span ═ (D90-D10)/D50; wherein D10 is the particle size with a cumulative particle distribution of 10%; d50 is the particle size with a cumulative particle distribution of 50%; d90 is the particle size with a cumulative particle distribution of 90%.
The closed cell rate of the polyolefin resin foaming sheet to be radiated and crosslinked is more than 85 percent; too many holes can cause the sealing performance to be reduced, and the strength of the foam surface body is low, so that the foam surface body is broken when being impacted, and the foam surface body is not suitable for being used as a frame sealing material. The crosslinking density of the radiation crosslinking polyolefin resin foam sheet is more than 15% and within 70%, preferably 20-65%, and more preferably 20-58%. The polyolefin has a certain strength by itself after foaming, but the bulk strength becomes low after foaming. The strength reduction caused by blasting can be compensated to a certain extent by crosslinking, and the capability of the foaming material for enduring instantaneous impact is improved. The crosslinking degree is too low, the strength of the foamed material body is poor, and the impact resistance is too low; too high crosslinking degree, too high foam hardness, poor flexibility.
The known auxiliary agent is properly selected within the range of not influencing the excellent effects of toughness, gap following ability, light weight, high strength and the like of the obtained foaming material. Examples of the auxiliary include foaming aids, sensitizers, rheological agents, catalysts, lubricants, antioxidants, shrinkage inhibitors, heat stabilizers, light stabilizers, weather stabilizers, metal deactivators, UV absorbers, light stabilizers, antibacterial agents, mildewcides, plasticizers, flame retardants, tackifiers, colorants, antistatic agents, tension improvers and fluidity improvers. The above additives may be used alone, or two or more thereof may be used in combination.
Specific examples of the present invention and comparative examples are given below in tabular form, wherein the respective component content data are mass percentages of the total mass.
Example 1:
feeding 130g of first polyolefin resin (15 parts of LLDPE, 10 parts of POE), 130g of falling weight impact, 130g of second polyolefin resin (EVA15 parts of LDPE, 38.3 parts of LDPE), 2 parts of azodicarbonamide serving as a foaming agent, 0.4 part of zinc oxide serving as a catalyst and 10100.3 parts of antioxidant into an extruder, melting and mixing at 120 ℃, extruding into a sheet, performing high-energy electron irradiation crosslinking treatment on the sheet, wherein the crosslinking degree of the sheet is 10-70%, performing foaming process treatment on the crosslinked sheet at 185-300 ℃, heating the obtained foamed sheet, and performing stretching orientation and thinning treatment to obtain the crosslinked polyolefin foamed sheet.
Examples 2 to 6 and comparative examples 1 to 3:
the procedure of example 1 was repeated, except that the compounding of the polyolefin resin composition was changed as shown in tables 1 and 2, and the amount of the first resin in the crosslinking was adjusted as shown in tables 1 and 2, so that the falling weight impact of the first resin in comparative example 3 was 125 g.
Examples
Comparative example
The results show that the polyolefin foaming sheet can still maintain good toughness and space following capability under the condition of a thin thickness, and meets the application of a frame sealing material of an electronic product.
The test method of the invention is as follows:
dart impact test: the impact mass at 50% failure of a plastic film or sheet specimen was measured using the method of ASTM D1709A. The film adopts Hapro experiment tape casting equipment, the temperature is 190 ℃, the screw rotating speed is 50rpm, and the thickness of the prepared film is 31.8 +/-3 mu m; and (3) standing for 24 hours at the temperature of 23 +/-2 ℃ and testing the falling standard impact quality of the film according to the method of ASTM D1709A.
Apparent density test method: the test was carried out using the Archimedes principle, using the GB/T6343 method, using a Mettler Toledo model ME1040E instrument, taking the average of the three samples as the final result. The density of the foaming product is too low, the difference between the strength of the body of the foaming product and the strength of the resin is too large, and the loss of the strength of the body of the foaming material is too much. The foamed product has too high density, large integral hardness and insufficient flexibility, so that the gap following capability is low and the sealing performance is reduced.
Compressive strength of foam (i.e., foamed sheet): according to GB/T-8813 standard detection, foam is cut into standard sample blocks of 50mm x h, when the thickness of the foam is not enough, the foam is overlapped into a target thickness of 25mm +/-5 mm through multiple layers of foam, the initial compression amount is set, the sample is compressed at the speed of 5mm/min, meanwhile, the real-time compression strength is recorded, and when the compression amount reaches 50%, the compression strength is the required compression strength value. The compression stress is higher, the screen is easy to be pushed up when the screen is loaded after die cutting, the loading gap is too large, and the density performance is reduced.
FIG. 2 is a schematic structural diagram of the foamed sheet of the present invention, and it can be seen from the figure that the falling ball impact test: testing the corona on the two sides of the foam to be more than 42dyn, after the two sides are coated with glue, cutting the foam coated with the glue into a square frame with a certain shape by using a laser cutting machine, wherein the size of the square frame is 62X 0.7mm, adhering the foam-back-shaped frame on a perforated PC board, placing another PC board on the adhesive tape, pressing the PC board for 10 seconds by using a 5kg weight, standing the PC board for 24 hours at normal temperature, and then testing. The PC board was mounted on the equipment mounting frame (PC board with holes up and PC board down), the height of the pellet was adjusted, and the test was started. The steel ball (the quality of the steel ball can be changed along with the requirement of a customer) falls from a high position, the steel ball freely falls for 5 times from the height of 25mm, whether the PC board is peeled or not is observed, if the PC board is not peeled, the height is increased by 50mm, and the test is repeated until the PC board is peeled. The judgment basis is as follows: no drop of the PC board and no tear of the foam, marked as √ i; the foam body is broken and marked as 'x A'; failure between the foam and the adhesive layer was noted as "x B".
The crosslinking degree test method comprises the following steps: accurately weighing 0.1-1 g of a dry constant weight IXPE sample to 0.001 g; cutting into small pieces, coating with 120 mesh copper net, reflux extracting with xylene in Soxhlet extractor for 12h at boiling temperature, drying in oven at 60 deg.C for 12h to constant weight, and calculating crosslinking degree (G) according to the following formula: g ═ 100% (W1-W/W0-W). Wherein W0 is the total weight of the sample and the copper mesh before extraction, and W1 is the weight of the sample and the copper mesh after extraction and drying of the sample.
The closed pore rate test method comprises the following steps: cutting foam according to a certain size (on the premise of being parallel to the thickness direction, a section is formed in any direction, namely the section 1, taking any point on the section as an initial point, taking the point as the initial point, drawing a straight line on the section perpendicular to the thickness direction, taking a point 50mm away from the initial point on the straight line as an end point, respectively taking the initial point and the end point as initial points of a second third surface, forming a second section and a third section in the same way, forming four sections in the same way, wherein the four sections and the upper surface and the lower surface can jointly form a cuboid with the bottom side length of 50mm and the height of a square at the bottom of the thickness of the foam), weighing the cuboid as a mass m1, and the apparent volume as v 1. Placing the soaked cotton in water, completely immersing the soaked cotton in water, placing the soaked cotton in the water with the highest point 30mm or more away from the water surface, simultaneously placing the whole container filled with water in a vacuumizing device, keeping the vacuumizing device for 45min under the pressure of the relative vacuum degree of 0.04MPa, taking out the soaked cotton, absorbing water by using a paper towel, weighing m2, and then calculating the closed cell rate according to the formula: cell closed Cell ratio (ρ water v1+ m1-m2)/ρ water v 1. Rho water is the real-time density of water under the condition of test temperature, and can be known by inquiring a corresponding water and temperature density correspondence table.
The compression strength measuring method comprises the following steps: the compression strength of the foam is detected according to GB/T-8813 standard, the foam is cut into a standard sample block of 50mm x h, when the thickness of the foam is not enough, the foam is overlapped into a target thickness of 25mm +/-5 mm through multiple layers of foam, the initial compression amount is set, the sample is compressed at the speed of 5mm/min, the real-time compression strength is recorded, and the compression strength when the compression amount reaches 25 percent is the required compression strength value.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The crosslinked polyolefin foamed sheet is characterized in that the thickness of the foamed sheet is 0.01-0.5 mm, and the density is 0.3g/cm3～0.8g/cm3Compression set ofWhen the content is 50 percent, the compressive stress is less than or equal to 2MPa, when at least 60g of small balls fall from the height of more than 35mm, the foamed sheet body is not cracked, the closed cell rate is more than 85 percent, and the crosslinking degree is 15 to 70 percent.
2. The crosslinked polyolefin foamed sheet according to claim 1, wherein the raw material comprises a first polyolefin resin, a second polyolefin resin and a foaming agent, the first polyolefin resin is a polyolefin resin having a falling weight impact of 130g or more and is used in an amount of 8% or more based on the sum of the first polyolefin resin and the second polyolefin resin, and the first polyolefin resin and the second polyolefin resin have different properties.
3. The crosslinked polyolefin foamed sheet according to claim 2, wherein the first type of polyolefin resin comprises a vinyl resin obtained by copolymerizing an alpha olefin monomer having 3 to 8 carbon atoms with a vinyl monomer, and is obtained by gas phase polymerization or solution polymerization using a ziegler-natta catalyst, a metallocene catalyst, a bifunctional catalyst, or a catalyst containing aluminum, zirconium, iron, titanium, manganese, chromium, nickel, palladium or/and platinum metal elements, wherein the mass of the alpha olefin monomer is less than 30% of the total mass of all the monomers.
4. The crosslinked polyolefin foamed sheet according to claim 3, wherein the vinyl resin is one or more of an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-pentene copolymer, an ethylene-hexene copolymer and an ethylene-octene copolymer.
5. A crosslinked polyolefin foamed sheet according to claim 4, wherein the second polyolefin-based resin is one or more of polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, metallocene polyethylene, low molecular weight polyethylene, ultra-low molecular weight polyethylene, polyethylene wax, ethylene-propylene copolymer, ethylene-propylene terpolymer, polyvinyl acetate, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer.
6. The crosslinked polyolefin foamed sheet according to claim 5, wherein the first polyolefin resin has a melting point of 70 to 140 ℃, a melt index of 0.2 to 6.2g/10min under a 2.16Kg load at 190 ℃, and a density of 0.840 to 0.940g/cm3。
7. The crosslinked polyolefin foamed sheet according to claim 6, wherein the melting point of the second type polyolefin resin is 60 to 165 ℃ and the melt index of the second type polyolefin resin at 190 ℃ under a 2.16Kg load is 0.1 to 7.0g/10min, and the difference between the melt index of the second type polyolefin resin and the melt index of the first type polyolefin resin under the same conditions is not more than 5.0.
8. The crosslinked polyolefin foamed sheet according to claim 7, wherein the foaming agent comprises a physical foaming agent and a chemical foaming agent, wherein the physical foaming agent comprises one or more of nitrogen, carbon dioxide, butane or expanded microspheres, and the physical foaming agent is used for foaming by an extrusion or compression foaming process,
the chemical foaming agent comprises one or more of azodicarbonamide, 2 ' -azobisisobutyronitrile, diisopropyl azodicarboxylate, barium azodicarboxylate, diethyl azodicarboxylate, azoaminobenzene, nitroso compound, N ' -dimethyl-N, N ' -dinitrosoterephthalamide, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, p-toluenesulfonylsemicarbazide, 5-phenyltetrazole, trihydrazinotriazine, sodium bicarbonate, sodium carbonate, citric acid, sodium citrate, and hydrates thereof.
9. The crosslinked polyolefin foamed sheet according to claim 8, wherein the azodicarbonamide has a particle size of 2 to 50 μm and a distribution Span of 1.0 to 2.0.
10. The process for producing a crosslinked polyolefin foamed sheet according to claim 1, comprising the steps of:
s1: preparing different master batches, wherein the master batches comprise a foaming agent, resin, toner and an auxiliary agent, the resin comprises a first polyolefin resin and a second polyolefin resin, the first polyolefin resin is a polyolefin resin with the falling weight impact of more than or equal to 130g, the using amount of the first polyolefin resin is more than 8 percent of the mass sum of the first polyolefin resin and the second polyolefin resin,
the second polyolefin-based resin comprises one or more of the following: polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, metallocene polyethylene, low molecular weight polyethylene, ultra-low molecular weight polyethylene, polyethylene wax, ethylene-propylene copolymers, ethylene-propylene terpolymers, polyvinyl acetate, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, and ethylene-acrylic ester copolymers,
s2: mixing different master batches in advance, melting and extruding the mixture into sheets at the temperature of between 90 and 125 ℃,
s3: the sheet material in the step S2 is processed by high-energy electron irradiation crosslinking treatment, the crosslinking degree of the sheet material is 10-60 percent,
s4: the crosslinked sheet in the step S3 is subjected to foaming process treatment at a temperature of 185-300 ℃,
s5: and (4) heating the foamed sheet obtained in the step (S4), and performing stretching orientation and thinning treatment to obtain a crosslinked polyolefin foamed sheet.
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