CN117126519B - Foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties - Google Patents
Foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties Download PDFInfo
- Publication number
- CN117126519B CN117126519B CN202311390742.5A CN202311390742A CN117126519B CN 117126519 B CN117126519 B CN 117126519B CN 202311390742 A CN202311390742 A CN 202311390742A CN 117126519 B CN117126519 B CN 117126519B
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- antibacterial
- foaming
- radiation refrigeration
- passive radiation
- 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.)
- Active
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 121
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 121
- 238000005187 foaming Methods 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 66
- 239000011324 bead Substances 0.000 title claims abstract description 55
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 53
- 230000005855 radiation Effects 0.000 title claims abstract description 49
- 238000005057 refrigeration Methods 0.000 title claims abstract description 47
- 229920000728 polyester Polymers 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 18
- 239000002667 nucleating agent Substances 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 229920001225 polyester resin Polymers 0.000 claims abstract description 8
- 239000004645 polyester resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims abstract description 4
- -1 glycidyl methacrylate compound Chemical class 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 15
- 229940070527 tourmaline Drugs 0.000 claims description 12
- 229910052613 tourmaline Inorganic materials 0.000 claims description 12
- 239000011032 tourmaline Substances 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 8
- 229940123208 Biguanide Drugs 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229930182843 D-Lactic acid Natural products 0.000 claims description 4
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229940022769 d- lactic acid Drugs 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 241001330002 Bambuseae Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- CVXKJCHSXFOPDP-UHFFFAOYSA-N [Fe].[Li].[Mg] Chemical compound [Fe].[Li].[Mg] CVXKJCHSXFOPDP-UHFFFAOYSA-N 0.000 claims description 3
- GFORUURFPDRRRJ-UHFFFAOYSA-N [Na].[Mn] Chemical compound [Na].[Mn] GFORUURFPDRRRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 229920000229 biodegradable polyester Polymers 0.000 claims description 3
- 239000004622 biodegradable polyester Substances 0.000 claims description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229920002101 Chitin Polymers 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 229940100890 silver compound Drugs 0.000 claims description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical class COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 150000003379 silver compounds Chemical class 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 40
- 238000001816 cooling Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000013538 functional additive Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 235000014121 butter Nutrition 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000003889 chemical engineering Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229920006327 polystyrene foam Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000008223 sterile water Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241001360526 Escherichia coli ATCC 25922 Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006381 polylactic acid film Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 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
- C08J9/16—Making expandable particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3415—Heating or cooling
- B29C44/3426—Heating by introducing steam in the mould
-
- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/232—Forming foamed products by sintering expandable particles
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- 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)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a foaming polylactic acid bead material with passive radiation refrigeration and antibacterial performance, which comprises an inner foaming polylactic acid layer and an outer antibacterial polyester layer, wherein the inner layer comprises 70-90wt% of polylactic acid resin, 0.1-5wt% of chain extender, 0.05-0.5wt% of nucleating agent and 0.1-5wt% of infrared functional auxiliary agent, the pore diameter of the inner layer is 30-150 mu m, the outer layer comprises 78-99wt% of polyester resin, 0-10wt% of hydrolysis inhibitor and 1-10wt% of antibacterial agent, the outer layer accounts for 3-20% of the total mass of the foaming polylactic acid bead, and the thickness of the outer layer is 5-30 mu m. The porous structure of the material can effectively perform multiple reflection and scattering on incident sunlight, reduce solar radiation absorption, simultaneously has higher infrared emissivity in the wavelength range of 8-14 mu m, can effectively reduce the temperature of the surface and the environment of the material, and has excellent antibacterial performance.
Description
Technical Field
The invention relates to the technical field of foaming polylactic acid materials, in particular to a foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties.
Background
The high-temperature weather in summer brings a plurality of inconveniences to the life and work of human beings, and the traditional cooling mode uses refrigeration equipment such as an air conditioner, a fan and the like to cool the living and working places of the human beings, but a large amount of electric power energy is consumed, and resource waste is greatly caused.
The passive radiation refrigeration technology depends on the characteristic performance of the material, reflects most sunlight in the wave band of 0.25-2.5 mu m, and simultaneously emits heat in the material out by infrared light wave with the wavelength of 8-14 mu m after the heat is vibrated and absorbed by atomic bonds of the material, so that the aim of cooling is fulfilled. Because passive radiation refrigeration does not need energy input, no pollution is caused, and the ambient temperature can be effectively reduced, the passive radiation refrigeration is considered to be an ideal choice for replacing an energy-intensive refrigeration mode at the present stage, and can be widely applied to the building field (such as roofs, walls, windows and the like), vehicles, electrical equipment, wearable equipment and the like.
However, the passive radiation refrigeration material at the present stage is mainly applied to the surface of a substrate needing cooling in the form of a coating or a covering film, and the application field is quite limited. The invention creatively combines the passive radiation refrigeration technology with the bead foaming technology, provides the passive radiation refrigeration foaming polylactic acid bead material which has the advantages of continuous production, controllable cost, good refrigeration effect and antibacterial property, and can greatly widen the application field of the passive radiation refrigeration material.
Disclosure of Invention
Aiming at the situation, the invention provides the foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties, and the foaming material is combined with the infrared functional auxiliary agent, so that on one hand, the porous structure of the foaming material can effectively perform multiple reflection and scattering on incident sunlight to reduce solar radiation absorption, and on the other hand, the infrared functional auxiliary agent can ensure that the material has higher infrared emissivity in the wavelength range of 8-14 mu m, thereby effectively reducing the temperature of the surface of the material and the environment. In addition, the foaming polylactic acid material also has excellent antibacterial performance. The passive radiation refrigeration foaming polylactic acid bead material can be formed into various molded parts with different sizes and special shapes by steam die pressing, so that the application range is greatly widened, and the refrigeration and cooling requirements of special application scenes are met.
In order to achieve the above purpose, the present invention provides the following technical solutions: the foaming polylactic acid bead material with passive radiation refrigeration and antibacterial performance comprises a foaming polylactic acid inner layer and an antibacterial polyester outer layer wrapped on the surface of the foaming polylactic acid inner layer, wherein the foaming polylactic acid inner layer comprises 70-90wt% of polylactic acid resin, 0.1-5wt% of chain extender, 0.05-0.5wt% of nucleating agent and 0.1-5wt% of infrared functional auxiliary agent, the infrared functional auxiliary agent is at least one of high-temperature bamboo charcoal, magnesium iron lithium tourmaline, sodium manganese tourmaline, calcium magnesium tourmaline, bragg tourmaline and aluminum ferric salt, the pore diameter of the foaming polylactic acid inner layer is 30-150 mu m, the antibacterial polyester outer layer comprises 78-99wt% of polyester resin, 0-10wt% of hydrolysis inhibitor and 1-10wt% of antibacterial agent, and the outer layer accounts for 3-20% of the total mass of the foaming polylactic acid bead, and the thickness of the outer layer is 5-30 mu m.
Further, the cell pore size of the inner layer of the foamed polylactic acid is 50 to 130. Mu.m, more preferably 50 to 100. Mu.m.
For the expanded polylactic acid beads with the same expansion ratio, the addition amount of the nucleating agent directly determines the pore size of the inner cells of the expanded polylactic acid and also determines the molding property of the expanded beads and the refraction and reflection properties of the expanded beads on the radiated light, thereby influencing the passive radiation refrigeration property of the material. When the addition amount of the nucleating agent exceeds 0.5%, more crystal nuclei exist in the polylactic acid, and these crystal nuclei generate small and dense cells, and the cell size tends to be less than 30. Mu.m. Although the radiated light undergoes multiple reflections and refractions inside the expanded beads at this time, the internal pressure is relieved too quickly before the beads are molded due to the small cells, resulting in poor molding properties of the expanded beads and molded articles exhibiting "friability". On the contrary, when the addition amount of the nucleating agent is less than 0.05%, although the number of cells is reduced, the cells are larger, the pressure maintaining property is better, and the molding property becomes better, the refraction and reflection times of the radiation light inside the foaming beads are reduced, and the passive radiation refrigeration effect is weakened.
Further, the polylactic acid resin in the inner layer of the foaming polylactic acid is one or more of L-lactic acid homopolymer, D-lactic acid homopolymer and copolymer of L-lactic acid and D-lactic acid, the melt index is 3-5g/10min (190 ℃,2.16 kg), the melting point is more than or equal to 145 ℃, the tensile modulus is more than or equal to 3000MPa, and the tensile strength is more than or equal to 40MPa. The lower melt index can provide necessary viscosity and melt strength, ensure the formation of a closed cell structure of the polylactic acid in the foaming process, and reduce the broken porosity.
Further, the chain extender in the inner layer of the foaming polylactic acid is glycidyl methacrylate compound containing epoxy functional groups or glycidyl acrylate compound containing epoxy functional groups. The chain extender can improve the molecular weight and branching degree of the polylactic acid, thereby improving the melt strength and further reducing the porosity of the foamed polylactic acid.
Further, the particle size of the infrared functional auxiliary agent is 100-900nm, more preferably 200-600nm, still more preferably 300-500nm. The excessive particle size can lead to serious shrinkage of the cell size of the foaming polylactic acid, and the molding property of the beads is poor, thereby affecting the mechanical property of the material. The agglomeration easily occurs in the processing process when the particle size is too small.
Further, the foaming polylactic acid inner layer also contains 1-5wt% of compatilizer and/or 0.01-1wt% of antioxidant and/or 0.01-1wt% of lubricant.
Further, the compatilizer is a silane coupling agent, higher fatty acid, unsaturated organic acid and the like. The silane coupling agent is preferably vinyl trimethoxy silane, vinyl triethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, methyl triethoxy silane, etc. The alkoxy hydrolysis at one end of the silane coupling agent can react with the inorganic infrared functional auxiliary agent to form a chemical bond, and the lipophilic group at the other end can intertwine with the molecular chain of the polylactic acid, so that the interfacial capability between the organic and inorganic materials is improved. Under the action of the high-shearing high-rotation-speed double screws, the infrared functional auxiliary agent can be more uniformly dispersed in the polylactic acid base material.
Further, the nucleating agent is one or more of talcum powder, zinc borate, polytetrafluoroethylene powder, barium sulfate, calcium carbonate and glass fiber, and preferably glass fiber. The nucleating agent needs to have certain incompatibility with the polylactic acid base material, so that the growth of cells at the junction of the nucleating agent and the polylactic acid is promoted, and the heterogeneous nucleation effect is achieved. Meanwhile, the nucleating agent also has the functions of reducing foaming pressure and homogenizing cells. In addition, compared with other nucleating agents, the glass fiber has lower water absorption, better hydrophobicity in the foaming process and can effectively reduce the degradation of polylactic acid.
Further, the polyester resin in the outer layer of the antibacterial polyester is biodegradable polyester, the melt index of the polyester resin is 3-5g/10min (190 ℃,2.16 kg), the melting point is less than or equal to 130 ℃, the Vicat softening point is more than or equal to 90 ℃, the tensile strength is more than or equal to 25MPa, and the elongation at break is more than or equal to 500%. The biodegradable polyester is preferably one or more of polyethylene succinate, polybutylene adipate and polybutylene adipate/terephthalate copolymer, more preferably polybutylene adipate/terephthalate copolymer. During the molding process, when a relatively low vapor pressure acts on the expanded polylactic acid beads, the low-melting polyester resin is rapidly melted at a low temperature, but the high-melting polylactic acid of the core layer is not melted, so that the cell structure is maintained. During the subsequent cooling process, the beads are welded to each other by rapid cooling of the outer layer polyester resin, resulting in a molded article. However, it should be noted that the melting point of the polyester of the outer layer must not be too low (not less than 100 ℃) which would otherwise tend to cause the outer layer resin to melt too rapidly to form a closed layer, impeding the adequate entry of steam heat into the interior of the expanded polylactic acid beads, causing internal "pinch-in" of the article, resulting in a lower degree of cure.
Further, the thickness of the antibacterial polyester outer layer is 5-30 mu m. If the outer layer is too thin, the fusion between the beads is insufficient, and the fusion strength is lowered; if the outer layer is too thick, for the same density of expanded beads, the ratio of the expanded inner layer is reduced, thereby leading to a reduction in the number of cells inside the expanded beads, a reduction in the number of times of refraction and emission of the radiated light in the porous structure, and a reduction in the passive radiation refrigerating effect of the material. Meanwhile, when infrared rays emitted from the inside of the foaming beads penetrate through the thicker outer layer and radiate to the external environment, a part of heat is conducted to the thicker unfoamed outer layer, the total heat radiated to the outside is reduced, and the cooling effect is further weakened.
Further, the hydrolysis inhibitor in the outer layer of the antibacterial polyester is preferably one or more of glycidyl ether, triglycidyl isocyanate and diamine carbide, and more preferably diamine carbide. The hydrolysis resistance agent generally reacts with the carboxyl end groups of the polyester, and effectively plays a role in blocking and inhibiting hydrolysis.
Further, the antibacterial agent in the outer layer of the antibacterial polyester is one or more of nano silver powder, nano silver compound, nano zinc powder, nano zinc oxide, nano copper oxide, monoammonium phosphate, lithium ferrite, nano titanium dioxide, vanillin derivative, anilide compound, quaternary ammonium salt compound, biguanide compound, chitin, castor oil and the like. Preferably, the antibacterial agent is a composite antibacterial agent of inorganic nano silver-zinc powder and organic biguanide compound (silver-zinc biguanide composite antibacterial agent). The silver zinc biguanide compound antibacterial agent has better antibacterial capability and safety than a single inorganic or organic antibacterial agent. In addition, the composite antibacterial agent is only added on the outer surface layer of the foaming polyester, so that the surface of the foaming product has excellent antibacterial effect, the addition amount of the antibacterial agent is reduced to the greatest extent, and the cost is reduced. And the antibacterial agent is only added on the outer non-foaming layer, so that the influence on the cell structure and the cell size of the inner layer caused by the introduction of the antibacterial agent can be avoided.
Further, the antibacterial polyester outer layer also contains 0.01-1wt% of antioxidant and/or 0.01-1wt% of lubricant.
Further, the antioxidant is one or more of hindered phenols, hindered amines, phosphites and the like, and is preferably 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenylmethyl) benzene.
Further, the lubricant is one or a mixture of more than one of oleamide, erucamide, stearic acid monoglyceride and vinyl distearamide, and is preferably erucamide. The lubricant can increase the fluidity of the polylactic acid in the extrusion process, so that the production is more continuous and stable.
The invention also provides a foaming polylactic acid molding product with passive radiation refrigeration and antibacterial performance, which is obtained by adopting the foaming polylactic acid bead material with the passive radiation refrigeration and antibacterial performance through water vapor sintering molding. Has higher infrared emissivity in the wavelength range of 8-14 mu m, can effectively reduce the temperature of the surface and the environment of the material, and has excellent antibacterial performance.
A preparation method of a foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties comprises the following steps:
step one, uniformly mixing raw materials of the foamed polylactic acid inner layer, then putting the raw materials into an extruder I, uniformly mixing raw materials of the antibacterial polyester outer layer, and then putting the raw materials into an extruder II; the speed of the mixer is preferably 200 revolutions per minute, and the mixing time is preferably 30 minutes;
and step two, connecting the extruder I and the extruder II through a die so as to realize coextrusion. Simultaneously starting the extruder I and the extruder II to carry out coextrusion so that the material extruded by the extruder II is wrapped on the surface of the material extruded by the extruder I, and adjusting the extrusion rate of the extruder I and the extruder II so that the mass ratio of the extruded material of the extruder I to the extruded material of the extruder II is 80:20-97:3, wherein the extrusion temperature is preferably 200-250 ℃;
step three, granulating the co-extruded strand silk by a high-speed granulator to prepare polylactic acid particles with the particle length of 2.0-2.5mm and the single weight of 1.0-1.5 mg;
and fourthly, adding the polylactic acid particles, a certain amount of deionized water, kaolin and butter into a closed high-pressure reaction kettle with a stirring function, introducing carbon dioxide into the kettle, raising the temperature and continuously stirring materials, opening a valve at the lower part of the reaction kettle when the temperature in the kettle is raised to 120-170 ℃ and the pressure in the kettle is raised to 2-4MPa, instantly discharging the polylactic acid particles out of the kettle, and under the action of a huge pressure difference, instantly escaping the carbon dioxide which is originally infiltrated in the polylactic acid particles, generating phase separation, and enabling the particles to rapidly expand, thereby finally obtaining the foamed polylactic acid beads with passive radiation refrigeration and antibacterial properties.
Further, in the fourth step, 1-100 parts by mass of polylactic acid particles, 1-200 parts by mass of deionized water, 1-5 parts by mass of kaolin and 1-3 parts by mass of butter are formed in the reaction kettle.
The method for preparing the foaming polylactic acid product by adopting the foaming polylactic acid beads comprises the following steps: the foamed polylactic acid beads are added into a closed pressure tank, and compressed air is introduced to raise the pressure in the pressure tank to 0.5-6kg. After maintaining the set pressure for 12 hours, the foamed polylactic acid beads were injected into a mold, and high-temperature steam was introduced so that the surface of the foamed beads was sintered, but the cell structure inside the beads was maintained. And then cooling water is introduced, and the foaming polylactic acid product can be obtained after demoulding. And (3) baking the foamed polylactic acid part in a baking room to obtain a finished product of the foamed polylactic acid part with stable size and passive radiation refrigeration and antibacterial properties.
Further, the steam pressure of the sintered foaming polylactic acid beads is 0.5-2kg, the sintering time is 1-20 seconds, the cooling water temperature is normal temperature, and the cooling time is 10-150s.
Further, the temperature of the drying room is 70-80 ℃, and the time for baking the products is more than 6 hours.
The beneficial effects of the invention are as follows: the foaming polylactic acid beads and the molded product combine the porous structure of the foaming material with the infrared functional auxiliary agent, and can effectively reduce the temperature of the surface of the material and the environment. Compared with the unfoamed material without cells, the porous structure of the foamed polylactic acid material has the function of isolating heat, and can also effectively perform multiple reflection and scattering on incident sunlight, so that solar radiation absorption is greatly reduced, and the temperature of the surface of the material is reduced. The carbon-oxygen single bond, carbon-oxygen double bond, carbon-carbon bond and carbon-hydrogen bond contained in the polylactic acid foaming material have strong bond vibration capability, can absorb and radiate more infrared heat energy, and achieve better cooling effect. In addition, due to the addition of the infrared functional auxiliary agent, the material has higher infrared emissivity in the wavelength range of 8-14 mu m, and can further effectively reduce the temperature of the surface and the environment of the material, thereby achieving the purpose of passive radiation refrigeration. The infrared nano functional auxiliary agent is prepared by an adding method in the extrusion section, so that the problem of the efficiency of secondary construction of a coating method is avoided, and the problem of reduced passive radiation refrigeration effect caused by the damage of the surface infrared coating due to the aging and the damage of the surface infrared coating can be avoided. On the other hand, the surface of the foaming polylactic acid material also has excellent antibacterial and mildew-proof properties, when the foaming polylactic acid material is used as a material for roofs, walls and the like in the field of construction, the mildew rate of the roofs and the walls of the construction can be greatly reduced, and the foaming polylactic acid material can be further expanded in the fields of wearable equipment, sports and fitness and the like.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is an external view of a foamed polylactic acid bead having passive radiation refrigeration and antimicrobial properties of the present invention;
FIG. 2 is an external view of a molded plate of foamed polylactic acid having passive radiation refrigeration and antibacterial properties according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
uniformly mixing polylactic acid A (manufactured by Nature Works Co., ltd., USA), glycidyl methacrylate chain extender containing epoxy functional groups (manufactured by Basiff Co., ltd., germany), infrared functional additive aluminum ferric sulfate salt with average particle size of 400nm (manufactured by Hangzhou three-wire chemical engineering Co., ltd., marked as infrared additive a), compatibilizer vinyl trimethoxysilane coupling agent KH171 (manufactured by Hangzhou Jikka chemical engineering Co., ltd.), nucleating agent glass fiber (manufactured by Hangzhou three-wire chemical engineering Co., ltd.), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene antioxidant (manufactured by Basiff Co., ltd., germany), erucamide lubricant (manufactured by He Co., ltd.) according to a mass ratio of 89.85:3:5:1:0.15:0.5:0.5:0.5, and then feeding the mixture into an extruder I; polyester B (manufactured by Zhejiang Huafeng group), diamine carbide hydrolysis resistant agent (manufactured by Italon (Tianjin) synthetic materials Co., ltd.), silver zinc biguanide compound antibacterial agent (manufactured by Buddha science and technology Co., ltd.), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxy benzyl) benzene antioxidant (manufactured by Basiff company, germany), erucamide lubricant (manufactured by He group Co., ltd.) are mixed according to a mass ratio of 87:2:10:0.5: and (3) uniformly mixing 0.5, putting the mixture into a second extruder, adjusting the extrusion rate of the first extruder and the second extruder to ensure that the mass ratio of extrusion materials is 90:10, cooling and granulating the strand silk into expandable polylactic acid composite particles with the length of 2.0-2.5mm and the single weight of 1.0-1.5 mg.
100 parts by mass of the obtained expandable polylactic acid composite particles, 200 parts by mass of deionized water, 1.5 parts by mass of kaolin and 3 parts by mass of butter are added into a high-pressure reaction kettle, heated and filled with carbon dioxide for pressurization, and the pressure is instantaneously relieved at the temperature of 128.5 ℃ and the pressure of 3.5Mpa, so that polylactic acid composite foaming beads with the bulk density of 40-45g/L are obtained.
The polylactic acid composite expanded beads prepared above were put into a pressure tank, and the pressure was maintained at a pressure of 2.0kg for 8 hours. The polylactic acid composite expanded beads were then filled into a large complex metal mold, and the surface of the expanded beads was subjected to continuous high-temperature compression molding with a steam pressure of 1.0kg for 15 seconds. And after sintering, introducing cooling water for 80s, and finally demolding to obtain the polylactic acid foaming product with passive radiation refrigeration and antibacterial properties.
Example 2:
except that the material formula of the inner layer of the foaming polylactic acid is adjusted to be polylactic acid A, a chain extender, an infrared functional additive aluminum ferric sulfate salt, a compatilizer vinyl trimethoxy silane coupling agent, a nucleating agent glass fiber, an antioxidant and a lubricant in a mass ratio of 93.85:3:1:1:0.15:0.5:0.5, a passive radiation refrigeration polylactic acid foaming product is prepared by adopting the same method as in the example 1.
Examples 3 to 7:
the same method as in example 1 was used to prepare a passive radiation refrigeration polylactic acid foamed article, except that the infrared functional auxiliary agent in the inner layer of foamed polylactic acid was replaced with high temperature bamboo charcoal, magnesium iron lithium tourmaline, sodium manganese tourmaline, calcium magnesium tourmaline, and bragg tourmaline (all manufactured by Hangzhou three-wire chemical engineering limited, respectively denoted as infrared auxiliary agent b, c, d, e, f).
Example 8:
a passive radiation refrigeration polylactic acid foamed article was prepared by the same method as in example 1, except that the infrared functional auxiliary agent was replaced with an aluminum ferric sulfate salt (produced by hangzhou three-wire chemical engineering ltd.) having an average particle diameter of 800 nm.
Example 9:
except that the material formula of the outer layer of the antibacterial polyester is adjusted to be polyester B, a diamine carbide hydrolysis-resistant agent, a silver-zinc biguanide composite antibacterial agent, an antioxidant and a lubricant with the mass ratio of 95:2:2:0.5:0.5 except for the above, a passively radiation-cooled polylactic acid foamed article was produced in the same manner as in example 1.
Comparative example 1:
the same method as in example 1 was used to prepare a passive radiation refrigeration polylactic acid foamed article, except that the infrared functional auxiliary agent, aluminum ferric sulfate, was not added to the material of the foamed polylactic acid inner layer.
Comparative example 2:
a passive radiation refrigeration polylactic acid foamed article was prepared by the same method as in example 1, except that the infrared functional aid was replaced with an aluminum ferric sulfate salt (produced by hangzhou three-wire chemical engineering ltd.) having an average particle diameter of 1200 nm.
Comparative example 3:
a passively radiation-cooled polylactic acid-foamed article was produced in the same manner as in example 1, except that the thickness of the outer layer of the antibacterial polyester was adjusted to 80 μm.
Comparative example 4:
except that the material formula of the inner layer of the foaming polylactic acid is adjusted to be polylactic acid A, a chain extender, an infrared functional additive aluminum ferric sulfate salt, a compatilizer vinyl trimethoxy silane coupling agent, a nucleating agent glass fiber, an antioxidant and a lubricant in a mass ratio of 89.99:3:5:1:0.01:0.5:0.5, a passive radiation refrigeration polylactic acid foaming product is prepared by adopting the same method as in the example 1.
Comparative example 5:
polylactic acid and an auxiliary agent are blended, extruded and pelletized according to the formula of example 1, hot pressed into tablets by a flat vulcanizing machine without foaming treatment, and a solid plate is produced.
Comparative example 6:
the same method as in example 1 was used to prepare a passively radiation-cooled polylactic acid foamed article, except that no antimicrobial agent was added to the material of the outer layer.
And detecting infrared spectrums of the prepared polylactic acid foaming products, testing the reflectances of different wave bands by using a Lambda1050 spectrometer of a polytetrafluoroethylene coating integrating sphere, and calculating the emissivity.
And (3) detecting the refrigerating performance of the prepared polylactic acid foaming product, and placing a copper plate with a thermocouple temperature sensor on a polystyrene foam plate with a groove size of 10 x 5 cm. The copper plate is covered with polylactic acid foaming sample blocks with the size of 10 x 2.5cm, and is covered with a polyethylene preservative film to shield the influence of heat convection. The entire polystyrene foam board is wrapped with aluminum foil to shield the surrounding environment from radiation. Before the building is innovated in the Linan area Mo Ma in Hangzhou, zhejiang province at 4 months of 2023, the change of temperature is tested and recorded from 10 am to 2 pm (the solar power on the day is 320-670W/m) 2 ) And the temperature difference between the covered polylactic acid foam board and the uncovered polylactic acid foam board was calculated.
The prepared polylactic acid foaming product is subjected to antibacterial detection, and according to QB/T2591-2003A antibacterial property test method and antibacterial effect of antibacterial plastics, the detection bacteria are escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538. The swatches were immersed in hot water at 50 ℃ for 16 hours before antimicrobial testing. The test steps are as follows: and (3) sterilizing the sample to be tested by using 75% ethanol, airing, and diluting the strain into a bacterial suspension with proper concentration by using sterile water for standby. 0.2mL of the bacterial suspension was dropped on the surface of the sample, and a polylactic acid film (4.0 cm. Times.4.0 cm) with a thickness of 0.1mm was applied thereto, so that a uniform liquid film was formed between the sample and the film. The culture is carried out for 18 to 24 hours at 37 ℃ with a relative humidity of 90 percent. The bacterial liquid is washed down by sterile water, diluted into proper concentration gradient, and 0.1mL of the bacterial liquid is evenly coated on the prepared sterile agar medium. The cells were incubated at 37℃for 18 to 24 hours, and the results were observed. The negative control was replaced with a sterile dish and the other operations were the same.
The raw material formulations and performance tests of examples 1-9 and comparative examples 1-6 are shown in tables 1 and 2, respectively.
TABLE 1
TABLE 2
As can be seen from examples 1, 2 and comparative example 1, as the amount of the infrared functional additive aluminum ferric sulfate increases, the emissivity of the foamed polylactic acid product in the light wave band of 8-14 μm gradually increases, and the cooling performance of the foamed polylactic acid product also increases. When the adding amount of the ferric aluminum sulfate is 5 parts, the average emissivity of the 8-14 mu m light wave band is up to 89%, the average temperature difference with the environment can reach more than 5 ℃, and the cooling effect is obvious.
As can be seen from examples 3-7, different kinds of infrared functional adjuvants were tested. Experiments show that the foaming polylactic acid materials containing different infrared functional additives have strong passive radiation refrigeration effects.
It can be seen from examples 1, 8 and comparative example 2 that when the particle size of the infrared functional auxiliary agent is greater than 900nm, the cell size of the foamed polylactic acid beads is reduced, the molding property of the foamed beads is affected, more pinholes are formed on the surface of the product, the curing degree of the product is lower, and the mechanical property is weaker.
As can be seen from example 1 and comparative example 3, when the outer polyester skin layer is thicker, the cell structure inside the beads is smaller, the number of times of refraction and reflection of the radiated light is reduced, and the refrigerating and cooling performance of the material is reduced. Meanwhile, when infrared rays emitted from the inside of the foaming beads penetrate through the thicker outer layer and radiate to the external environment, a part of heat is conducted to the thicker unfoamed outer layer, the total heat radiated to the outside is reduced, and the cooling effect is further weakened.
It can be seen from examples 1 and comparative example 4 that too small an amount of the nucleating agent added results in a decrease in the number of cells, and as such, the number of refraction and reflection of the radiated light decreases, and the refrigerating and cooling performance of the material decreases.
As can be seen from the examples 1 and 5, the non-foamed polylactic acid material has higher infrared emissivity although it contains the infrared functional auxiliary agent, but the material has poorer refrigerating and cooling effects because the interior has no cell structure and cannot refract and reflect incident light for a plurality of times.
As can be seen from examples 1, 9 and comparative example 6, the use of the antibacterial agent provides the foamed article with a good antibacterial effect, and the antibacterial rate of the formed foamed article against escherichia coli and staphylococcus aureus gradually increases as the amount of the antibacterial agent increases.
Claims (9)
1. The foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties is characterized by comprising a foaming polylactic acid inner layer and an antibacterial polyester outer layer wrapped on the surface of the foaming polylactic acid inner layer, wherein the foaming polylactic acid inner layer comprises 70-90wt% of polylactic acid resin, 0.1-5wt% of chain extender, 0.05-0.5wt% of nucleating agent and 0.1-5wt% of infrared functional auxiliary agent, the infrared functional auxiliary agent is at least one of high-temperature bamboo charcoal, magnesium-iron-lithium tourmaline, sodium-manganese tourmaline, calcium-magnesium tourmaline, bragg tourmaline and aluminum-ferric sulfate, the particle size of the infrared functional auxiliary agent is 100-900nm, the pore size of the foaming polylactic acid inner layer is 30-150 mu m, the antibacterial polyester outer layer comprises 78-99wt% of polyester resin, 0-10wt% of hydrolysis inhibitor and 1-10wt% of antibacterial agent, the antibacterial polyester outer layer accounts for 3-20% of the total mass of the foaming polylactic acid bead, and the thickness of the antibacterial polyester outer layer is 5-30 mu m.
2. The expanded polylactic acid bead material with passive radiation refrigeration and antibacterial properties according to claim 1, wherein: the pore diameter of the foam polylactic acid inner layer is 50-130 mu m.
3. The expanded polylactic acid bead material with passive radiation refrigeration and antibacterial properties according to claim 1, wherein: the polylactic acid resin in the foamed polylactic acid inner layer is one or more of L-lactic acid homopolymer, D-lactic acid homopolymer and copolymer of L-lactic acid and D-lactic acid, and the melt index of the polylactic acid resin measured under the conditions of 190 ℃ and 2.16kg is 3-5g/10min, the melting point is more than or equal to 145 ℃, the tensile modulus is more than or equal to 3000MPa, and the tensile strength is more than or equal to 40MPa.
4. The expanded polylactic acid bead material with passive radiation refrigeration and antibacterial properties according to claim 1, wherein: the chain extender in the inner layer of the foaming polylactic acid is glycidyl methacrylate compound containing epoxy functional groups or glycidyl acrylate compound containing epoxy functional groups.
5. The expanded polylactic acid bead material with passive radiation refrigeration and antibacterial properties according to claim 1, wherein: the foaming polylactic acid inner layer also contains 1-5wt% of compatilizer and/or 0.01-1wt% of antioxidant and/or 0.01-1wt% of lubricant.
6. The expanded polylactic acid bead material with passive radiation refrigeration and antibacterial properties according to claim 1, wherein: the polyester resin in the outer layer of the antibacterial polyester is biodegradable polyester, the melt index measured at 190 ℃ and 2.16kg is 3-5g/10min, the melting point is less than or equal to 130 ℃, the Vicat softening point is more than or equal to 90 ℃, the tensile strength is more than or equal to 25MPa, and the elongation at break is more than or equal to 500%.
7. The expanded polylactic acid bead material with passive radiation refrigeration and antibacterial properties according to claim 1, wherein: the antibacterial polyester outer layer also contains 0.01-1wt% of antioxidant and/or 0.01-1wt% of lubricant.
8. The expanded polylactic acid bead material with passive radiation refrigeration and antibacterial properties according to claim 1, wherein: the antibacterial agent is one or more of nanometer silver powder, nanometer silver compound, nanometer zinc powder, nanometer zinc oxide, nanometer copper oxide, monoammonium phosphate, lithium ferrite, nanometer titanium dioxide, vanillin derivative, anilide compound, quaternary ammonium salt compound, biguanide compound, chitin and castor oil.
9. A foaming polylactic acid molding product with passive radiation refrigeration and antibacterial performance is characterized in that: the foamed polylactic acid bead material with passive radiation refrigeration and antibacterial properties according to any one of claims 1 to 8 is obtained by water vapor sintering molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311390742.5A CN117126519B (en) | 2023-10-25 | 2023-10-25 | Foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202311390742.5A CN117126519B (en) | 2023-10-25 | 2023-10-25 | Foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties |
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| JP2014162799A (en) * | 2013-02-21 | 2014-09-08 | Toray Ind Inc | Polylactic acid-based mulching film |
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| CN110615975A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Antibacterial and mildewproof polylactic acid composition, foaming bead, preparation method of foaming bead and formed body |
| CN112175371A (en) * | 2020-10-29 | 2021-01-05 | 浙江农林大学 | Manufacturing process of antibacterial flame-retardant carbon-plastic composite material |
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| EP2334719A2 (en) * | 2008-10-09 | 2011-06-22 | Synbra Technology B.V. | Particulate, expandable polymer, method for producing particulate expandable polymer, as well as a special use of the obtained foam material |
| JP2014162799A (en) * | 2013-02-21 | 2014-09-08 | Toray Ind Inc | Polylactic acid-based mulching film |
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