CN112266590B - Polylactic acid/microcrystalline cellulose composite foamed sheet and preparation method thereof - Google Patents
Polylactic acid/microcrystalline cellulose composite foamed sheet and preparation method thereof Download PDFInfo
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- CN112266590B CN112266590B CN202010990602.1A CN202010990602A CN112266590B CN 112266590 B CN112266590 B CN 112266590B CN 202010990602 A CN202010990602 A CN 202010990602A CN 112266590 B CN112266590 B CN 112266590B
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- polylactic acid
- microcrystalline cellulose
- agent
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- foaming
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 71
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 71
- 229920000168 Microcrystalline cellulose Polymers 0.000 title claims abstract description 40
- 235000019813 microcrystalline cellulose Nutrition 0.000 title claims abstract description 40
- 239000008108 microcrystalline cellulose Substances 0.000 title claims abstract description 40
- 229940016286 microcrystalline cellulose Drugs 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005187 foaming Methods 0.000 claims abstract description 24
- 239000004014 plasticizer Substances 0.000 claims abstract description 23
- 239000002667 nucleating agent Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000004088 foaming agent Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical group CC(C)C1=CC=CC(C(C)C)=C1N=C=NC1=C(C(C)C)C=CC=C1C(C)C XLDBGFGREOMWSL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical group FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 abstract description 8
- 230000006835 compression Effects 0.000 abstract description 8
- 239000006260 foam Substances 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 3
- 238000005452 bending Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 6
- 235000010980 cellulose Nutrition 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- -1 alkane halide Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- 229920005692 JONCRYL® Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 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 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- LNYGCDOWFJXOSW-UHFFFAOYSA-N 1-n,3-n,5-n-tricyclohexylbenzene-1,3,5-tricarboxamide Chemical compound C=1C(C(=O)NC2CCCCC2)=CC(C(=O)NC2CCCCC2)=CC=1C(=O)NC1CCCCC1 LNYGCDOWFJXOSW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- RZSJYVBYLBNFGQ-UHFFFAOYSA-N difluoromethane hydrochloride Chemical compound FCF.Cl RZSJYVBYLBNFGQ-UHFFFAOYSA-N 0.000 description 1
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 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 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- VYXPIEPOZNGSJX-UHFFFAOYSA-L zinc;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Zn+2].[O-]P([O-])(=O)C1=CC=CC=C1 VYXPIEPOZNGSJX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- C08J9/12—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 physical blowing agent
- C08J9/14—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 physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
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)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides a polylactic acid/microcrystalline cellulose composite foamed sheet, which comprises the following raw materials in parts by weight: 5-45 parts of microcrystalline cellulose, 40-80 parts of polylactic acid, 2-15 parts of plasticizer, 0.3-10 parts of nucleating agent, 2-3 parts of maleic anhydride, 0.2-3 parts of anti-hydrolysis agent and 0.1-1 part of cross-linking agent; the invention also provides a preparation method of the foaming sheet. The polylactic acid/microcrystalline cellulose composite foamed sheet prepared by the invention has good compression resistance, bending resistance, heat preservation performance and the like, the stability of foam pores is further improved after the microcrystalline cellulose is added, the foam pores are more uniformly distributed, the product cost is further reduced, and a finished product can be widely applied to the fields of tableware, food packaging, express packaging and the like. The polylactic acid/microcrystalline cellulose composite foaming sheet prepared by the invention has the foaming multiplying power of 5-40 times, preferably 15-25 times, and the heat-resistant temperature of 130 ℃.
Description
Technical Field
The invention belongs to the field of biodegradable materials of bio-based sources, and relates to preparation of a polylactic acid/microcrystalline cellulose composite material foamed sheet.
Background
Polylactic acid is a fully biodegradable material derived from renewable resources. The lactic acid is prepared by fermenting cassava, corn, beet and the like, and the product can be decomposed into carbon dioxide and water under the action of microorganisms and water oxygen in soil after being discarded, so that the lactic acid is a green low-carbon environment-friendly material in a true sense, can partially replace traditional plastics from petroleum sources, and radically solves the problem of white pollution. The polylactic acid has no toxic or side effect and no harmful substance release, and is an ideal food contact safe packaging material.
Cellulose is the most abundant renewable and biodegradable high molecular polymer in nature, and mainly comes from plants. Compared with common cellulose, the microcrystalline cellulose has larger chemical reaction activity, larger specific surface area, high crystallinity, high strength and the like.
CN 107383434A discloses a preparation method of a cellulose nanocrystal reinforced polylactic acid foam material, which is to blend cellulose nanocrystals and polylactic acid in an organic solvent, dry the solvent to obtain a cellulose nanocrystal/polylactic acid composite material, and perform supercritical carbon dioxide foaming on the cellulose nanocrystal/polylactic acid composite material by using a supercritical carbon dioxide foaming method. This patent needs to use the solvent, then stoving solvent, and the processing mode is complicated, influences the environment.
CN 109651783A discloses a micro-foamed natural fiber reinforced polylactic acid composite material and a preparation method thereof, wherein the natural fiber reinforced polylactic acid composite material is prepared by using natural fiber modified polylactic acid, and then micro-porous injection molding foaming molding is carried out by an injection molding machine; the compatibility of the natural fiber and the polylactic acid adopted by the patent is poor, and the injection molding machine is adopted for foaming and molding, so that the production efficiency is low.
Disclosure of Invention
The invention provides a preparation method of a polylactic acid/microcrystalline cellulose composite foamed sheet, which realizes the following purposes: the prepared composite foamed sheet has the advantages that the stability of the foam holes is improved, and the distribution of the foam holes is more uniform; the compression resistance and the folding endurance are improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a polylactic acid/microcrystalline cellulose composite foamed sheet comprises the following raw materials in parts by weight:
5-45 parts of microcrystalline cellulose, 40-80 parts of polylactic acid, 2-15 parts of plasticizer, 0.3-10 parts of nucleating agent, 2-3 parts of maleic anhydride, 0.2-3 parts of anti-hydrolysis agent and 0.1-1 part of cross-linking agent.
The following is a further improvement of the above technical scheme:
the foamed sheet comprises the following raw materials in parts by weight:
15-34 parts of microcrystalline cellulose, 54-75 parts of polylactic acid, 6-9 parts of plasticizer, 0.3-1 part of nucleating agent, 2-3 parts of maleic anhydride, 0.2-0.5 part of anti-hydrolysis agent and 0.4-0.6 part of cross-linking agent.
A preparation method of a polylactic acid/microcrystalline cellulose composite foamed sheet comprises the steps of drying, mixing, extruding, granulating and foaming.
And in the mixing step, the microcrystalline cellulose, the nucleating agent, the maleic anhydride, the cross-linking agent and the hydrolysis resistant agent are firstly premixed uniformly to obtain premixed solid powder, and the polylactic acid and the plasticizer or the mixture of the polylactic acid and the plasticizer are respectively added and mixed uniformly.
The preparation method of the mixture of the polylactic acid and the plasticizer comprises the steps of adding the plasticizer into polylactic acid particles and stirring until the surface of the polylactic acid is uniformly wetted, so as to obtain the mixture of the polylactic acid and the plasticizer.
And (3) extruding and granulating, wherein the rotation frequency of a screw extruder is 23-27Hz, and the processing temperature is 150-190 ℃.
And in the extrusion granulation, the temperature of each area from the feed inlet to the extrusion outlet is respectively as follows:
150-160℃、160℃、165℃、170℃、175-185℃、185-190℃、190℃、190℃、175-180℃、165-170℃。
and adding the foamed and granulated granules into a double-screw extruder, and adding a foaming agent, wherein the injection amount of the foaming agent is 5-8.5L/h, and the rotation frequency of a screw for injecting the foaming agent is 17-25Hz.
The screw rotating frequency of the double-screw extruder and the first-stage extruder is 24-26Hz; the processing temperature is 175-200 ℃; the rotation frequency of a screw of the secondary extruder is 16-20Hz; the processing temperature is 140-185 ℃.
The temperature of the first-stage extruder from the feed inlet to the discharge outlet is respectively 165-175 ℃, 170-180 ℃, 185-190 ℃, 190-200 ℃ and 190-200 ℃;
the temperature of the secondary extruder from the feed inlet to the discharge outlet is 180-185 ℃, 175-180 ℃, 170-175 ℃, 160-165 ℃, 150-155 ℃, 145-150 ℃, 140-145 ℃ and 130-140 ℃ respectively.
Drying, namely drying the polylactic acid and the microcrystalline cellulose at 70-90 ℃ for 1-12h; preferably at 80 ℃ for 4h.
The plasticizers include, but are not limited to: one or more of tributyl citrate, triethyl citrate, citric acid, glycerol, diethylene glycol, glycerol triacetate, dioctyl phthalate, ethylene glycol, propylene glycol, sorbitol, pentaerythritol, acetyl tributyl citrate, epoxidized soybean oil, propylene glycol adipate, diisononyl adipate, dioctyl maleate, polypropylene glycol, polyethylene glycol and polyvinyl alcohol; preferably polyethylene glycol and tributyl citrate;
such blowing agents include, but are not limited to: carbon dioxide, nitrogen, argon, oxygen, alkane halide, sodium bicarbonate, calcium bicarbonate, azodicarbonamide, azodiisobutyronitrile and diisopropyl azodicarboxylate; preferably difluoromethane chloride;
such nucleating agents include, but are not limited to: inorganic nucleating agents, talc, montmorillonite, silica, titanium dioxide, amide nucleating agents (e.g., ethylene bis stearamide EBS, TMC-328 or CZ500, etc.), hydrazide nucleating agents (e.g., TMC-300, CHC-300 or TMC-306, etc.), organic phosphate nucleating agents (e.g., zinc phenylphosphonate, sanulant TMHK162 or Sanulant TMHK160, etc.); preferably TMC-300 and talcum powder;
the crosslinking agent includes, but is not limited to, one or more of the group consisting of 1, 4-butanediol, 1, 4-butane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, octadecyl isocyanate, polymethylene polyphenyl polyisocyanates, and diphenylmethane diisocyanates, ADR series by basf corporation; preferably ADR 4370S, joncryl ADR 4370S;
the hydrolysis resistant agent comprises one or more of triethyl phosphite, dihydroxypropyl octadecanoic acid, polycarbodiimide compounds, monocarbodiimide compounds, bismonocarbodiimide compounds and acrylic copolymers with epoxy groups; bis (2,6-diisopropylphenyl) carbodiimide is preferred.
The foaming agent is added, the gas foaming agent is added in a high-pressure injection mode, the solid foaming agent is added through the powder feeding barrel, the polylactic acid foaming sheet is continuously produced, the foaming multiplying power is 5-40 times adjustable, and the heat-resistant temperature can reach 130 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polylactic acid/microcrystalline cellulose composite foamed sheet prepared by the invention has good compression resistance, bending resistance, heat preservation performance and the like, the stability of foam pores is further improved after the microcrystalline cellulose is added, the foam pores are more uniformly distributed, the product cost is further reduced, and a finished product can be widely applied to the fields of tableware, food packaging, express packaging and the like.
(2) The polylactic acid/microcrystalline cellulose composite foamed sheet prepared by the invention has the foaming multiplying power of 5-40 times, preferably 15-25 times, the heat-resistant temperature of 130 ℃, the tensile strength (TD) of 525-820 kPa, the tensile strength (MD) of 714-968 kPa,
elongation at break (TD) of 3.0-5.1%, elongation at break (MD) of 5.6-8.2%; tear Strength (TD) of 2.7-4.7 kN/m, tear Strength (MD) of 1.9-3.6 kN/m.
(3) The polylactic acid/microcrystalline cellulose composite foamed sheet prepared by the invention has good compression resistance and folding resistance, and the high deformation rate is 2.4%.
Detailed Description
The examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the claims, as other alternatives will occur to those skilled in the art and are within the scope of the invention.
Example 1 preparation method of polylactic acid/microcrystalline cellulose composite foamed sheet
The foaming sheet comprises the following raw material components in parts by weight:
the plasticizer is polyethylene glycol;
the nucleating agent is TMC-300;
the cross-linking agent is ADR 4370S;
the anti-hydrolysis agent is bis (2,6-diisopropylphenyl) carbodiimide.
The preparation method of the foaming sheet comprises the following steps:
(1) Drying
Respectively drying polylactic acid and microcrystalline cellulose at 80 ℃ for 4h;
(2) Surface wetting
Weighing quantitative dried polylactic acid and plasticizer, adding the plasticizer into polylactic acid particles, and stirring until the surface of the polylactic acid is uniformly wetted to obtain a mixture of the polylactic acid and the plasticizer;
(3) Mixing
Uniformly premixing microcrystalline cellulose, a nucleating agent, maleic anhydride, a cross-linking agent and an anti-hydrolysis agent to obtain a premix; then, stirring the mixture of the polylactic acid and the plasticizer and the premix in a stirrer until the mixture is uniformly mixed;
(4) Extrusion granulation
Extruding and granulating by a double-screw extruder special for polylactic acid, wherein the processing temperature is 160-190 ℃, and obtaining the granules of the polylactic acid/microcrystalline cellulose composite material.
The rotation frequency of the screw extruder was 25Hz, and the temperatures in the zones from the feed inlet to the extrusion outlet were: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 185 ℃, 190 ℃, 175 ℃ and 165 ℃.
(5) Foaming
Drying the granules of the polylactic acid/microcrystalline cellulose composite material at 80 ℃ for 4h, continuously extruding and foaming the granules by a primary double-screw continuous extrusion foaming device special for polylactic acid, adding the polylactic acid/microcrystalline cellulose composite material through main feeding, adding a foaming agent, wherein the amount of the foaming agent is determined by combining the requirement of a target product with the foaming ratio actually tested and adjusting the rotating frequency of the injection amount of the main screw and the foaming agent, the processing temperature of a primary extruder is between 165 and 190 ℃, the processing temperature of a secondary extruder is between 130 and 180 ℃, and continuously producing the polylactic acid foamed sheet to obtain the whole roll of foamed sheet.
The injection amount of the foaming agent is 5L/h;
the foaming agent is difluorochloromethane;
the rotational frequency of the injection amount of the foaming agent is 17Hz;
the screw rotation frequency of the primary extruder of the screw extruder is 25Hz, and the screw rotation frequency of the secondary extruder is 18Hz;
the primary extruder temperatures were, respectively (° c): 165. 170, 185, 190 190, 190;
the temperatures of the secondary extruders were (. Degree. C.) respectively: 180. 175, 170, 160, 150, 145, 140, 130;
the temperature sequence is from the feed inlet to the discharge outlet.
EXAMPLE two preparation method of polylactic acid/microcrystalline cellulose composite foamed sheet
The foaming sheet comprises the following raw material components in parts by weight:
the plasticizer is tributyl citrate;
the nucleating agent is talcum powder;
the cross-linking agent is Joncryl ADR 4370S;
the anti-hydrolysis agent is bis (2,6-diisopropylphenyl) carbodiimide;
the preparation method of the composite foamed sheet comprises the following steps:
(1) Drying
The polylactic acid and the microcrystalline cellulose are respectively dried for 4h at 80 ℃.
(2) Mixing
Weighing a certain amount of microcrystalline cellulose, a nucleating agent, maleic anhydride, a cross-linking agent and an anti-hydrolysis agent in proportion, and premixing uniformly to obtain premixed solid powder; adding polylactic acid particles through a main feeding barrel of the double-screw extruder, adding a plasticizer through liquid feeding of the double-screw extruder, and adding premixed solid powder through a solid auxiliary material feeding barrel of the double-screw extruder.
(4) Extrusion granulation
And extruding and granulating by a double-screw extruder special for polylactic acid to obtain granules of the polylactic acid/microcrystalline cellulose composite material.
The feeding speed of the polylactic acid particles is 27kg/h; the feeding speed of the plasticizer is 4kg/h; the feed rate of the solid auxiliary material was 19kg/h.
The temperature of each area of the double-screw extruder from the feed inlet to the discharge outlet is respectively as follows: 150 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 185 deg.C, 190 deg.C, 180 deg.C, 170 deg.C.
(5) Foaming
Drying the granules of the polylactic acid/microcrystalline cellulose composite material at 80 ℃ for 4 hours, continuously extruding and foaming the granules by using a secondary double-screw rod special for polylactic acid, adding the polylactic acid/microcrystalline cellulose composite material through main feeding, adding a foaming agent, wherein the amount of the foaming agent is determined by combining the requirement of a target product and the actually tested foaming ratio and adjusting the rotating frequency of the injection amount of the main screw rod and the foaming agent, the temperature of a first area is 175-200 ℃, the temperature of a second area is 140-185 ℃, and continuously producing a polylactic acid foamed sheet to obtain a whole roll of foamed sheet.
The rotational frequency of the injection amount of the foaming agent is 25Hz;
the rotation frequency of the screw of the primary extruder is 25Hz;
the temperatures of the primary extruder from the feed inlet to the discharge outlet are respectively (DEG C): 175. 180, 190, 200;
the rotation frequency of the screw of the secondary extruder is 18Hz;
the temperatures of the secondary extruder from the feed inlet to the discharge outlet are respectively (DEG C): 185. 180, 175, 165, 155, 150, 145, 140;
the injection amount of the foaming agent is 8.5L/h;
the blowing agent is difluorochloromethane.
The above test data were obtained by cutting foamed sheets into test strips.
The foamed sheets prepared in examples 1 and 2 above have the characteristics of improved bubble stability, more uniform bubble distribution, high pressure resistance and folding resistance.
GB 18006.1-2009 section 6.9.2 is adopted to detect heat resistance, and the result is: no deformation, defect, leakage and abnormality;
the detection method of the compression resistance comprises the following steps:
opening the cover of the sample box, horizontally placing the opening on a smooth surface, taking plate glass with the thickness of 3mm and the thickness of 10mm larger than each side of the opening, placing the plate glass on the sample, adding 1.5 +/-0.01 kg of static load (including the plate glass), measuring the middle points of any two pairs of edges by using a ruler with the precision of 1mm, taking the average value as the original height, then adding 2 +/-0.01 kg of weight, taking the average value of the heights measured at the same two points in 30s as the stressed height of the sample, and simultaneously observing whether the sample is broken or not.
The height deformation ratio was calculated according to the following formula:
in the formula: w is the overall compression height deformation,%;
h0 is the original height of the sample, mm;
h is the pressed height of the sample, mm.
According to the method, the compression resistance is detected, and the detection result of the compression resistance is as follows: the height deformation rate was 2.4%, and the sample was not cracked;
the method for testing the folding endurance comprises the following steps: open and shut 25 times with the sample, the angle of opening and shutting is 180 degrees, observes between box body and the lid broken line department and has or not fracture, and the testing result is: no fracture.
Claims (1)
1. The polylactic acid/microcrystalline cellulose composite foamed sheet is characterized by comprising the following raw material components in parts by weight: 75 parts of polylactic acid, 15 parts of microcrystalline cellulose, 7 parts of plasticizer, 0.3 part of nucleating agent, 2 parts of maleic anhydride, 0.4 part of cross-linking agent and 0.3 part of hydrolysis resistant agent;
the plasticizer is polyethylene glycol; the nucleating agent is TMC-300; the cross-linking agent is ADR 4370S; the anti-hydrolysis agent is bis (2,6-diisopropylphenyl) carbodiimide;
the preparation method of the polylactic acid/microcrystalline cellulose composite foamed sheet comprises the following steps:
(1) Drying
Respectively drying polylactic acid and microcrystalline cellulose at 80 ℃ for 4h;
(2) Surface wetting
Weighing quantitative dried polylactic acid and plasticizer, adding the plasticizer into polylactic acid particles, and stirring until the surface of the polylactic acid is uniformly wetted to obtain a mixture of the polylactic acid and the plasticizer;
(3) Mixing
Uniformly premixing microcrystalline cellulose, a nucleating agent, maleic anhydride, a cross-linking agent and an anti-hydrolysis agent to obtain a premix; then, stirring the mixture of the polylactic acid and the plasticizer and the premix in a stirrer until the mixture is uniformly mixed;
(4) Extrusion granulation
Extruding and granulating by a polylactic acid double-screw extruder at the processing temperature of 160-190 ℃ to obtain granules of the polylactic acid/microcrystalline cellulose composite material;
the rotation frequency of the screw extruder was 25Hz, and the temperatures in the zones from the feed inlet to the extrusion outlet were: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 185 ℃, 190 ℃, 175 ℃ and 165 ℃;
(5) Foaming
Drying granules of the polylactic acid/microcrystalline cellulose composite material at 80 ℃ for 4h, continuously extruding and foaming the granules by a polylactic acid secondary double-screw extruder, adding the polylactic acid/microcrystalline cellulose composite material through main feeding, adding a foaming agent, wherein the amount of the foaming agent is determined by regulating the rotation frequency of the injection amount of the main screw and the foaming agent according to the requirement of a target product and combining the foaming ratio actually tested, the processing temperature of a primary extruder is between 165 and 190 ℃, the processing temperature of a secondary extruder is between 130 and 180 ℃, and continuously producing a polylactic acid foamed sheet to obtain a whole roll of foamed sheet;
the injection amount of the foaming agent is 5L/h; the foaming agent is difluorochloromethane; the rotational frequency of the injection amount of the foaming agent is 17Hz;
the screw rotation frequency of the first-stage extruder is 25Hz, and the screw rotation frequency of the second-stage extruder is 18Hz; the temperature of the first-stage extruder is respectively as follows: 165 ℃, 170 ℃, 185 ℃, 190 ℃ and 190 ℃. 190 ℃, 190 ℃; the temperatures of the secondary extruder were: 180 ℃, 175 ℃, 170 ℃, 160 ℃, 150 ℃, 145 ℃, 140 ℃ and 130 ℃;
the temperature sequence is from the feed inlet to the discharge outlet.
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