CN112063139A - Polylactic acid modified material for food contact injection molding product and preparation method thereof - Google Patents
Polylactic acid modified material for food contact injection molding product and preparation method thereof Download PDFInfo
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- CN112063139A CN112063139A CN202010818517.7A CN202010818517A CN112063139A CN 112063139 A CN112063139 A CN 112063139A CN 202010818517 A CN202010818517 A CN 202010818517A CN 112063139 A CN112063139 A CN 112063139A
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- polylactic acid
- epoxidized
- coupling agent
- acid modified
- modified material
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 113
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 37
- 235000013305 food Nutrition 0.000 title claims abstract description 23
- 238000001746 injection moulding Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000008187 granular material Substances 0.000 claims abstract description 7
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 claims description 31
- 229920001434 poly(D-lactide) Polymers 0.000 claims description 27
- 239000007822 coupling agent Substances 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 18
- -1 polybutylene succinate Polymers 0.000 claims description 17
- 239000004014 plasticizer Substances 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 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 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 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 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003549 soybean oil Substances 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 235000012222 talc Nutrition 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 6
- 239000008158 vegetable oil Substances 0.000 claims description 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- 239000002383 tung oil Substances 0.000 claims description 3
- FKHKSWSHWLYDOI-UHFFFAOYSA-N 2-phenylbenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C=2C=CC=CC=2)=C1 FKHKSWSHWLYDOI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 claims description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 239000002285 corn oil Substances 0.000 claims description 2
- 235000005687 corn oil Nutrition 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 2
- 229960001826 dimethylphthalate Drugs 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920006228 ethylene acrylate copolymer Polymers 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010665 pine oil Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims 9
- 229920001432 poly(L-lactide) Polymers 0.000 claims 9
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 4
- 238000002715 modification method Methods 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 description 23
- 239000004033 plastic Substances 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 3
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 101150096185 PAAS gene Proteins 0.000 description 1
- 229920001273 Polyhydroxy acid Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920000118 poly(D-lactic acid) Polymers 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 239000010902 straw Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention belongs to the technical field of high polymer materials, and particularly discloses a polylactic acid modified material for manufacturing food contact injection molding products, and a preparation method thereof. The polylactic acid modified material is prepared from polylactic acid, inorganic mineral powder, a toughening agent and an auxiliary agent. Firstly, mixing polylactic acid, a toughening agent and an auxiliary agent to obtain a component A, and extruding the component A by a double-screw unit to obtain a molten component A; and mixing the molten component A with inorganic mineral powder in a double-screw unit, and then extruding, cooling and granulating to obtain the polylactic acid modified granular material. The invention provides a simple, efficient and low-cost polylactic acid toughening and heat-resistant modification method, and has important significance for the marketization of injection products of polylactic acid.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polylactic acid modified material for manufacturing food contact injection molding products, and also relates to a preparation method thereof.
Background
The plastic product has the advantages of low cost, strong plasticity and the like, and is widely applied in national economy. At present, plastics are widely applied to agriculture, industry, building, packaging, national defense and daily life of people. The plastic brings convenient and fast life style to people, so the dependence of people on the plastic is increased continuously. However, the environmental problems caused by plastics are becoming more serious, because the current plastics are mainly petroleum-based plastics which are made of petroleum, have non-regenerability, can hardly be degraded in the environment, can exist in the environment all the time, and cause serious environmental pollution and ecological damage. In order to reduce the damage to the environment while not influencing the conventional convenient life, the green plastic is used for replacing the conventional non-renewable petroleum-based plastic, so that the green plastic becomes a preferred scheme.
The green plastic is a plastic product which is harmless to human and environment. The research on green high polymer materials is popular in 80-90 years of the 20 th century, and natural high polymer starches, celluloses, chitin and modified high polymer compounds thereof are applied to the field of degradable plastics. Compared with limited petrochemical resources, the green plastic raw material can be synthesized only through photosynthesis of plants, and has sustainable availability and wide raw material sources.
For example, natural polysaccharides and modified compounds thereof can be processed into degradable disposable films, sheets, containers, foamed products, and the like by means of blending modification with general-purpose plastics, and waste thereof can be gradually hydrolyzed into small molecular compounds through intervention of natural polysaccharide macromolecule degrading enzymes such as amylase widely existing in the natural environment, and finally decomposed into pollution-free carbon dioxide and water to return to biospheres. Through continuous technical innovation, the chemical synthesis type biodegradable polymer grows up, develops and magnifies, and plays a very important role in green plastics nowadays. The current commercialized chemical synthetic green plastics are mainly polyhydroxy acids, and polylactic acid (PLA) is the most representative of them. Polylactic acid (PLA) is used as a bio-based degradable material, is thermoplastic aliphatic polyester, has the capability of complete biodegradation, can be used as raw material sources of agricultural and forestry wastes (such as straw and wood powder) and starch-containing crops (such as corn and cassava), generates carbon dioxide and water after decomposition, has zero pollution to the environment, has carbon emission only 1/4-1/2 of petroleum-based plastics in the processing and production process, and can realize the environment-friendly concept of natural, green, environment-friendly and emission reduction of human life at present.
The physical and chemical properties of polylactic acid are similar to those of petroleum-based plastics such as Polystyrene (PS), polyethylene terephthalate (PET) and the like, and the polylactic acid can be directly used or compounded with other materials and then applied to various fields such as biological medicine, packaging, automobiles, electronics, 3D printing, daily necessities and the like through different molding processes (such as injection molding, extrusion, spinning and the like). Polylactic acid has the defects of large brittleness, poor toughness, low impact resistance, poor heat resistance, poor durability and the like, and generally needs to be modified by technical means such as blending, copolymerization, crosslinking and the like to achieve the purpose of improving or enhancing the mechanical property and the processing property of the polylactic acid so as to meet the requirement of practical application.
The injection molding is one of important production processes in the plastic product industry in China, the total amount of products in 2018 accounts for 37.2 percent of the total amount of plastic products in China, the products tend to increase year by year, injection molding daily necessities are a large class of injection molding products, and along with the prohibition of the injection molding by legislation of the European Union, the huge market demands give infinite possibility to green plastics. Polylactic acid is an important member of biomass green plastics, and due to the shortage of raw material market supply, the price of the polylactic acid is always high at present, which is promoted from 1.6 ten thousand yuan/ton in 2014 to 2.2-2.5 ten thousand yuan/ton in 2018, and the price of the polylactic acid is up to 3 ten thousand yuan/ton at present. The expensive price severely limits the application and scale development of the polylactic acid industry. The invention aims at the requirements of injection molding products, provides a polylactic acid modified high polymer material to promote the market production of polylactic acid injection molding products and further contribute to the sustainable development strategy, environmental protection, energy conservation and emission reduction.
Disclosure of Invention
The invention mainly solves the technical problem of providing a polylactic acid modified material for food contact injection molding products and also provides a preparation method thereof.
In order to solve the technical problems, the invention adopts a technical scheme that: a polylactic acid modified material for food contact injection molding products comprises the following raw materials in parts by weight:
as a preferred embodiment of the present invention, the polylactic acid is PLLA (levorotatory polylactic acid) and/or PDLA (dextrorotatory polylactic acid); when the polylactic acid is a mixture of PLLA and PDLA, the weight ratio of PLLA: PDLA (1-99): (99-1) mixing.
In a preferred embodiment of the present invention, the PLLA has an optical purity of 95 to 99.5%, a relative molecular weight of 5 to 30 ten thousand, and a melt flow index of 5 to 30g/10min at 190 ℃ under a weight of 2.16 kg.
In a preferred embodiment of the present invention, the PDLA has an optical purity of 95 to 99.5%, a relative molecular weight of 5 to 30 ten thousand, and a melt flow index of 5 to 30g/10min at 190 ℃ under a weight of 2.16 kg.
In a preferred embodiment of the present invention, the inorganic mineral powder is at least one of kaolin, diatomaceous earth, talc powder and calcium sulfate, preferably food grade talc powder having a particle size of 800 to 2500 meshes, and more preferably food grade talc powder having a particle size of 1250 meshes.
As a preferred embodiment of the invention, the toughening agent is any one or a mixture of several selected from ethylene-acrylate copolymers (such as EMA and EEA), polyacrylate polymers (such as PAA and PAAS), polyolefin elastomers (PTE), polybutylene succinate (PBS) and polybutylene adipate/terephthalate (PBAT).
As a more preferred embodiment of the invention, the toughening agent is poly (butylene adipate terephthalate) (PBAT), the relative molecular weight is 8 to 12 ten thousand, and the melt flow index is 5 to 20g/10min at 190 ℃ and under the weight pressure of 2.16 kg.
As a preferred embodiment of the invention, the auxiliary agent is any one or a mixture of several selected from an antioxidant, a plasticizer, a coupling agent and a compatilizer; more preferably, the auxiliary agent is formed by mixing an antioxidant, a plasticizer, a coupling agent and a compatilizer, and more preferably, the mass ratio of the antioxidant to the plasticizer to the coupling agent to the compatilizer is (0.5-2): (0.2-2): 0.2-2).
In a preferred embodiment of the present invention, the antioxidant is at least one selected from the group consisting of epoxy vegetable oil, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], phenyl-p-phenylenediamine, tris (nonylphenyl) phosphite, thiodipropylenedistearyl ester, and dilaurylthiodipropionate.
As a preferred embodiment of the present invention, the plasticizer is a phthalate ester or a citrate ester, the phthalate ester comprises at least one of dimethyl phthalate, diethyl phthalate, dibutyl phthalate and diamyl phthalate, and the citrate ester comprises tri-n-butyl citrate and/or acetyl tributyl citrate.
As a preferred embodiment of the present invention, the coupling agent is any one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, an aluminum-titanium composite coupling agent, and an aluminum-zirconium composite coupling agent.
As a preferred embodiment of the present invention, the compatibilizer is an ethylene maleic anhydride copolymer and/or an acrylic styrene copolymer.
As a more preferred embodiment of the present invention, the antioxidant is an epoxidized vegetable oil, and the epoxidized vegetable oil is at least one of epoxidized soybean oil, epoxidized castor oil, epoxidized coconut oil, epoxidized palm oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized corn oil, epoxidized sunflower oil, epoxidized pine oil, and epoxidized tung oil; more preferably, the antioxidant is Epoxidized Soybean Oil (ESO).
As a more preferred embodiment of the invention, the plasticizer is a citric acid ester, more preferably acetyl tributyl citrate (ATBC).
As a more preferred embodiment of the present invention, the coupling agent is a silane coupling agent, more preferably a silane coupling agent KH 550.
As a more preferred embodiment of the present invention, the compatibilizer is an acrylic styrene copolymer, and further preferably, the compatibilizer is ADR 4468.
As a preferred embodiment of the invention, the polylactic acid modified material is prepared from the following raw materials in parts by weight:
as a more preferred embodiment of the present invention, the polylactic acid modified material is prepared from the following raw materials in parts by weight:
as a preferred embodiment of the present invention, the polylactic acid modified material, wherein the polylactic acid is PLLA or PDLA or a blend of PLLA and PDLA; preferably, when the polylactic acid is a blend of PLLA and PDLA, the weight ratio of PLLA: PDLA (40-70): (60-30), more preferably PLLA: PDLA 60:40 and mixing.
As a preferred embodiment of the present invention, the talc is food grade talc, more preferably 1250 mesh food grade talc.
The invention also provides a preparation method of the polylactic acid modified material, which comprises the following steps:
mixing the polylactic acid with the toughening agent and the auxiliary agent to obtain a component A, and extruding the component A through a first twin-screw unit to obtain a molten component A;
and mixing the molten component A with inorganic mineral powder in a second double-screw machine set, and then extruding, cooling and granulating to obtain the polylactic acid modified granular material.
In a preferred embodiment of the present invention, the first twin-screw unit is divided into 10 zones, and the temperature of each zone is 155 to 160 ℃, 160 to 165 ℃, 165 to 170 ℃, 170 to 175 ℃, 175 to 180 ℃, 180 to 185 ℃, 185 to 190 ℃, 190 to 195 ℃ and 195 to 200 ℃ in sequence.
As a preferred embodiment of the invention, the second double screw machine set is divided into 10 zones, and the temperature of each zone is 195-200 ℃, 190-195 ℃, 185-190 ℃, 180-185 ℃, 175-180 ℃, 170-175 ℃, 175-180 ℃, 165-170 ℃, 160-165 ℃ and 160-165 ℃ in sequence.
The polylactic acid modified material provided by the invention can be used for preparing food contact injection molding products.
The invention is directed at food contact injection molding products, scientific selection and optimization are carried out on the formula, and the obtained polylactic acid modified particles are mainly used for production of food contact injection molding products.
In the aspect of raw material formula, poly adipic acid/butylene terephthalate (PBAT) is preferably adopted as a toughening agent, the PBAT and polylactic acid (PLA) are also degradable biological polyester, and can be decomposed to generate carbon dioxide and water, so that the environment is zero-pollution, and the environment-friendly and green advantages are realized; meanwhile, PBAT is easier to obtain and low in price, and the production cost of the polylactic acid modified material can be reduced. Epoxidized soybean oil and acetyl tributyl citrate also have the advantages of environmental protection and green. The toughening agent and the auxiliary agent, particularly the toughening agent, the antioxidant and the plasticizer can improve the weather resistance and the processability of the polylactic acid modified material. Meanwhile, when inorganic mineral substances such as talcum powder are added in a large proportion, the coupling agent such as silane coupling agent in the auxiliary agent can also strengthen the compatibility of the inorganic mineral substance filler and PLA, effectively avoid gaps and defects of a multiphase interface, and reduce the probability of agglomeration caused by high-proportion addition of the talcum powder. The talcum powder can be used as a filler and a nucleating agent in the polylactic acid modified material to take effect, and the heat resistance of the polylactic acid product can be obviously improved.
The polylactic acid modified material provided by the invention can be prepared by singly using levorotatory polylactic acid or singly using dextrorotatory polylactic acid or by mixing the levorotatory polylactic acid and the dextrorotatory polylactic acid in terms of the selection of polylactic acid. Preferably, the levorotatory polylactic acid and the dextrorotatory polylactic acid are mixed for use, the polylactic acid mixed system has the advantages of high crystallinity and high heat deformation resistance, and the physical properties of the prepared modified particle product are obviously enhanced. The use of the poly (D-lactic acid) alone has limitations in industrial production because the PDLA itself is amorphous and the material itself has high heat resistance, and the injection molded article obtained from the poly (lactic acid) has the highest heat resistance in terms of heat resistance, but the raw material source is limited.
The polylactic acid modified material provided by the invention has the raw materials meeting the requirements of GB 9685 one 2016 (national food safety Standard) food contact material and product additive use standard and meeting the mandatory requirements of national food safety, and the prepared polylactic acid modified particles meet the environmental protection and green requirements and simultaneously take the cost problems of raw material shortage, high price and the like into consideration.
The invention also provides a preparation method of the polylactic acid modified particles for the food contact injection molding product. Firstly, mixing polylactic acid with a toughening agent and an auxiliary agent to obtain a component A, and then mixing the component A with inorganic mineral powder to obtain polylactic acid modified particles. Specifically, polylactic acid is mixed with a toughening agent and an auxiliary agent to obtain a component A, and the component A is extruded by a first twin-screw unit to obtain a molten component A; and mixing the molten component A with inorganic mineral powder in a second double-screw machine set, and then extruding, cooling and granulating to obtain the polylactic acid modified granular material.
Before preparation, the raw materials need to be dried, so that the moisture of each raw material is controlled to be 200-500 ppm; if the raw materials are liquid, the raw materials need to be sealed and stored in a dry environment before use. Wherein the drying mode is preferably vacuum drying, the vacuum degree is-0.09 to-0.1 Mpa, the drying temperature is 70 to 90 ℃, and the drying time is 30 to 60 minutes.
Wherein, the grain cutting process is as follows: and (3) drawing the molten modified strips extruded by the second double-screw machine set, cooling, granulating and screening to obtain the polylactic acid modified particles. The diameter of the polylactic acid modified particles after screening is 2-5 mm.
According to the preparation method provided by the invention, the component A is extruded by the first double-screw unit without cooling, but the second double-screw unit is additionally arranged below the extrusion port of the first double-screw unit, and the component A molten strip extruded by the first double-screw unit is ensured to stably fall into the feed port of the second double-screw unit. And then mixing the molten component A with inorganic mineral powder in a region 1 of a second double-screw unit, completely mixing in a region 2-10 of the second double-screw unit, extruding, cooling and granulating to obtain the polylactic acid modified particles.
Because the steps of cooling, granulating and remelting the component A are omitted, the obtained component A in a molten state is directly mixed with the inorganic mineral powder and then granulated, the energy can be saved by more than 40 percent, and the production cost is obviously reduced.
The invention provides a simple, efficient and low-cost polylactic acid toughening and heat-resistant modification method, and has important significance for the marketization of injection molding products of polylactic acid.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described in detail by the following specific examples. The following examples are not specifically described, and all of the starting materials are commercially available.
Examples 1-10 are provided first, and are specifically shown in tables 1 and 2. Tables 1 and 2 show the raw material compositions of the polylactic acid modified materials provided in examples 1 to 4 and examples 5 to 10, respectively. Wherein the values in the tables all represent parts by weight.
Table 1 is specifically as follows.
TABLE 1
| Examples | PLLA | Talcum powder | PBAT | ESO | ATBC | KH550 | ADR4468 |
| 1 | 81 | 10 | 2 | 1.5 | 2 | 1.0 | 0.5 |
| 2 | 72 | 20 | 2 | 1.5 | 2 | 1.0 | 0.5 |
| 3 | 63 | 30 | 2 | 1.5 | 2 | 1.0 | 0.5 |
| 4 | 53.5 | 40 | 2 | 1.5 | 2 | 1.0 | 0.5 |
Table 2 is specifically as follows.
TABLE 2
The preparation method of the polylactic acid modified material in each embodiment comprises the following steps:
(1) mixing polylactic acid PLLA with a toughening agent and an auxiliary agent to obtain a component A, and extruding the component A through a first twin-screw unit to obtain a molten component A;
and mixing the molten component A with inorganic mineral powder in a second double-screw machine set, and then extruding, cooling and granulating to obtain the polylactic acid modified granular material.
Wherein the first twin-screw unit is divided into 10 zones, and the temperature of each zone is 155-160 ℃, 160-165 ℃, 165-170 ℃, 170-175 ℃, 175-180 ℃, 180-185 ℃, 185-190 ℃, 190-195 ℃ and 195-200 ℃ in sequence;
the second double-screw machine set is divided into 10 zones, and the temperature of each zone is 195-200 ℃, 190-195 ℃, 185-190 ℃, 180-185 ℃, 175-180 ℃, 170-175 ℃, 175-180 ℃, 165-170 ℃, 160-165 ℃ and 160-165 ℃ in sequence.
And then detecting the performance of the prepared polylactic acid modified material. The polylactic acid modified granular material prepared in each example is prepared into a sample strip by selecting a plastic mold according to GB/T9352-. The results are shown in Table 3.
TABLE 3
As can be seen from the performance test data of examples 1-4, the addition of talc powder can increase the impact strength of the modified particle product, reduce the elongation at break of the product, and have a tendency that the Vicat softening temperature is increased first and then decreased.
Compared with example 4, in example 5, the inorganic mineral powder is replaced by the talcum powder to be the calcium sulfate, the Vicat softening temperature of the product is reduced by 20 ℃, the reduction of the Vicat softening temperature indicates that the heat resistance is reduced, the product is unfavorable for containing hot meals, mainly, the calcium sulfate has no effect on crystallization in the polylactic acid mould, the crystallinity of the polylactic acid cannot be improved, namely, the heat resistance of the product cannot be improved, and therefore, the inorganic mineral powder is preferably the talcum powder.
Compared with example 4, in example 6, the toughening agent is replaced by the ethylene-methyl acrylate (EMA) with better toughening effect from PBAT, the elongation at break of the product is increased from 7.7% to 12.3%, and when the ethylene-acrylic ester copolymer is added into PLA to reach more than 10%, the elongation at break of the polylactic acid can be increased to more than 100%. However, for injection molded articles, the increase in elongation at break is not of practical significance, and considering that ethylene-acrylic acid ester copolymers are petroleum-based sources, it is preferred that the toughening agent be PBAT.
Compared with example 4, example 7 is that the antioxidant epoxidized soybean oil is replaced by epoxidized tung oil, and detection shows that the performance of the modified particles is not greatly influenced, but the epoxidized soybean oil has more advantages in terms of availability of raw materials and purchase cost.
Compared with example 4, in example 8, the plasticizer acetyl tributyl citrate is replaced by diethyl phthalate, and detection shows that the performance of the modified particles is slightly improved. However, from the beginning of formulation design, the selection of the more environment-friendly plasticizer ATBC is more in line with the consideration of safety because the probability of contacting with human body is high and the migration of the plasticizer is inevitable for living goods.
Compared with example 4, in example 9, the coupling agent KH550 is replaced by titanate, and detection shows that the performance of the modified particles is not improved as much as that of KH550 under the same use amount, which indicates that KH550 has better coupling effect on the inorganic filler and PLA compatible system than titanate.
Compared with example 4, in example 10, the chain extender ADR4468 is replaced by the ethylene maleic anhydride copolymer, and ST-1 of Shanghai province is selected, and detection shows that the performance of modified particles is not improved as much as that of ADR4468 under the same use amount, so that ADR4468 is preferred to be a compatilizer.
Examples 11, 12 are also provided. The raw material composition is specifically shown in table 4. Wherein the values in the tables all represent parts by weight. Table 4 is specifically as follows.
TABLE 4
| Examples | PLLA | PDLA | Talcum powder | PBAT | ESO | ATBC | KH550 | ADR4468 |
| 11 | 32.4 | 21.6 | 40 | 2 | 1.5 | 2 | 1.0 | 0.5 |
| 12 | 0 | 54 | 40 | 2 | 1.5 | 2 | 1.0 | 0.5 |
Example 11 polylactic acid feedstock was mixed using a weight ratio of PLLA to PDLA of 60:40 to create a PDLA/PLLA blend stereosystem.
Example 12 is the use of high purity PDLA.
And then detecting the performance of the prepared polylactic acid modified material. The polylactic acid modified granular materials prepared in the examples are prepared into sample strips, and 20s of crystallization is carried out in a mold on the sample strip preparation, the mold temperature is 105 ℃, and the detection results are shown in Table 5.
TABLE 5
Compared with example 4 using levorotatory polylactic acid (PLLA) alone, the performance data of example 11 shows that the physical properties of the polylactic acid modified particle product prepared by adopting the PDLA/PLLA blended stereo system are enhanced, and the impact strength is improved; the system has the characteristics of high crystallinity and high heat deformation resistance.
The performance test results of example 11 and example 12 also show that the heat resistance of the product is greatly improved as the content of PDLA is increased. Mainly, PDLA is amorphous, and the material itself has high heat-resistant deformation capacity, and PDLA has the highest heat resistance in terms of heat resistance of the product.
Claims (10)
1. The polylactic acid modified material for the food contact injection molding product is characterized by comprising the following preparation raw materials in parts by weight:
2. the polylactic acid-modified material according to claim 1, wherein the polylactic acid is PLLA and/or PDLA; when the polylactic acid is a mixture of PLLA and PDLA, the weight ratio of PLLA: PDLA (1-99): (99-1) mixing;
preferably, the PLLA has an optical purity of 95-99.5%, a relative molecular weight of 5-30 ten thousand, and a melt flow index of 5-30 g/10min at 190 ℃ under the pressure of a 2.16kg weight; and/or the PDLA has the optical purity of 95-99.5 percent, the relative molecular weight of 5-30 ten thousand and the melt flow index of 5-30 g/10min at 190 ℃ under the pressure of a 2.16kg weight.
3. The polylactic acid modified material according to claim 1, wherein the inorganic mineral powder is at least one of kaolin, diatomite, talc and calcium sulfate, preferably food grade talc with a particle size of 800-2500 meshes, and more preferably food grade talc with a particle size of 1250 meshes.
4. The polylactic acid modified material of claim 1, wherein the toughening agent is any one or a mixture of several selected from ethylene-acrylate copolymer, polyacrylate polymer, polyolefin elastomer, polybutylene succinate and polybutylene adipate/terephthalate; preferably, the toughening agent is poly (butylene adipate/terephthalate), the relative molecular weight is 8-12 ten thousand, and the melt flow index is 5-20 g/10min at 190 ℃ and under the weight pressure of 2.16 kg.
5. The polylactic acid modified material according to any one of claims 1 to 4, wherein the auxiliary agent is any one or a mixture of several of an antioxidant, a plasticizer, a coupling agent and a compatilizer; preferably, the auxiliary agent is formed by mixing an antioxidant, a plasticizer, a coupling agent and a compatilizer, and further preferably, the mass ratio of the antioxidant to the plasticizer to the coupling agent to the compatilizer is (0.5-2): (0.2-2): 0.2-2);
preferably, the antioxidant is selected from at least one of epoxy vegetable oil, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], phenyl-p-phenylenediamine, tris (nonylphenyl) phosphite, thiodipropylenedistearyl ester and dilaurylthiodipropionate; and/or the presence of a gas in the gas,
the plasticizer is phthalic acid ester or citric acid ester, the phthalic acid ester comprises at least one of dimethyl phthalate, diethyl phthalate, dibutyl phthalate and diamyl phthalate, and the citric acid ester comprises tri-n-butyl citrate and/or acetyl tributyl citrate; and/or the presence of a gas in the gas,
the coupling agent is any one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, an aluminum-titanium composite coupling agent and an aluminum-zirconium composite coupling agent; and/or the presence of a gas in the gas,
the compatilizer is ethylene maleic anhydride copolymer and/or acrylic acid styrene copolymer.
6. The polylactic acid modified material according to claim 5, wherein the antioxidant is an epoxidized vegetable oil, and the epoxidized vegetable oil is at least one of epoxidized soybean oil, epoxidized castor oil, epoxidized coconut oil, epoxidized palm oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized corn oil, epoxidized sunflower oil, epoxidized pine oil, and epoxidized tung oil; preferably, the antioxidant is epoxidized soybean oil; and/or the plasticizer is a citric acid ester, preferably the plasticizer is acetyl tributyl citrate; and/or the coupling agent is a silane coupling agent, preferably the coupling agent is KH 550; and/or the compatilizer is acrylic styrene copolymer, preferably, the compatilizer is ADR 4468.
7. The polylactic acid modified material according to any one of claims 1 to 6, which is prepared from the following raw materials in parts by weight:
preferably, the polylactic acid modified material is prepared from the following raw materials in parts by weight:
8. the polylactic acid modified material of claim 7, wherein the polylactic acid is PLLA or PDLA or a blend of PLLA and PDLA; preferably, when the polylactic acid is a blend of PLLA and PDLA, the weight ratio of PLLA: PDLA (40-70): (60-30), more preferably PLLA: PDLA 60:40, mixing; and/or the talcum powder is food grade talcum powder, and more preferably food grade talcum powder of 1250 meshes.
9. A method for preparing a polylactic acid modified material according to any one of claims 1 to 8, comprising the steps of:
mixing the polylactic acid with the toughening agent and the auxiliary agent to obtain a component A, and extruding the component A through a first twin-screw unit to obtain a molten component A;
mixing the molten component A with inorganic mineral powder in a second double-screw machine set, and then extruding, cooling and granulating to obtain a polylactic acid modified granular material;
preferably, the first twin-screw unit is divided into 10 zones, and the temperature of each zone is 155-160 ℃, 160-165 ℃, 165-170 ℃, 170-175 ℃, 175-180 ℃, 180-185 ℃, 185-190 ℃, 190-195 ℃ and 195-200 ℃ in sequence; and/or the presence of a gas in the gas,
the second double-screw machine set is divided into 10 zones, and the temperature of each zone is 195-200 ℃, 190-195 ℃, 185-190 ℃, 180-185 ℃, 175-180 ℃, 170-175 ℃, 175-180 ℃, 165-170 ℃, 160-165 ℃ and 160-165 ℃ in sequence.
10. Use of the polylactic acid modified material according to any one of claims 1 to 8 for preparing food contact injection molded articles.
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