CN113527765A - Polylactic acid composition and additive composition thereof, plastic product and preparation method thereof - Google Patents
Polylactic acid composition and additive composition thereof, plastic product and preparation method thereof Download PDFInfo
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- CN113527765A CN113527765A CN202110711946.9A CN202110711946A CN113527765A CN 113527765 A CN113527765 A CN 113527765A CN 202110711946 A CN202110711946 A CN 202110711946A CN 113527765 A CN113527765 A CN 113527765A
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- polylactic acid
- tert
- antioxidant
- bis
- butyl
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 101
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 98
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 239000000654 additive Substances 0.000 title claims abstract description 27
- 230000000996 additive effect Effects 0.000 title claims abstract description 27
- 229920003023 plastic Polymers 0.000 title claims abstract description 23
- 239000004033 plastic Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 64
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 64
- 239000002667 nucleating agent Substances 0.000 claims abstract description 40
- 239000003607 modifier Substances 0.000 claims abstract description 21
- 238000004806 packaging method and process Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 19
- -1 polyoxyethylene Polymers 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000001746 injection moulding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 7
- SBKRBXBQFDKYSO-UHFFFAOYSA-N (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C)=C(O)C(C(C)(C)C)=C1 SBKRBXBQFDKYSO-UHFFFAOYSA-N 0.000 claims description 6
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 claims description 6
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 6
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 6
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 6
- PTKQUKMXDNGKNS-UHFFFAOYSA-N P(=O)(O)(OP(=O)(O)O)C1CCC2(CCCCC2)CC1 Chemical compound P(=O)(O)(OP(=O)(O)O)C1CCC2(CCCCC2)CC1 PTKQUKMXDNGKNS-UHFFFAOYSA-N 0.000 claims description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 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 3
- GIOCILWWMFZESP-UHFFFAOYSA-N 2-hydroxyethyl butanoate Chemical compound CCCC(=O)OCCO GIOCILWWMFZESP-UHFFFAOYSA-N 0.000 claims description 3
- PFQAIMSYOXGWGG-UHFFFAOYSA-N N'-benzoylbenzohydrazide decanedioic acid Chemical compound C(C1=CC=CC=C1)(=O)NNC(C1=CC=CC=C1)=O.C(=O)(O)CCCCCCCCC(=O)O PFQAIMSYOXGWGG-UHFFFAOYSA-N 0.000 claims description 3
- MQKUGDKDFPFSDV-UHFFFAOYSA-N P(O)OPO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1 Chemical compound P(O)OPO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1 MQKUGDKDFPFSDV-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- XXHCQZDUJDEPSX-KNCHESJLSA-L calcium;(1s,2r)-cyclohexane-1,2-dicarboxylate Chemical compound [Ca+2].[O-]C(=O)[C@H]1CCCC[C@H]1C([O-])=O XXHCQZDUJDEPSX-KNCHESJLSA-L 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 229920000118 poly(D-lactic acid) Polymers 0.000 claims description 3
- 229920001434 poly(D-lactide) Polymers 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000003856 thermoforming Methods 0.000 claims description 3
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 2
- VVIKOPAXOBSMDD-UHFFFAOYSA-N P(OC1=C(C=C(C=C1)C1=CC=CC=C1)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)OC1=C(C=C(C=C1)C1=CC=CC=C1)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C.P(OC1=C(C=C(C=C1)C1=CC=CC=C1)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)OC1=C(C=C(C=C1)C1=CC=CC=C1)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C Chemical group P(OC1=C(C=C(C=C1)C1=CC=CC=C1)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)OC1=C(C=C(C=C1)C1=CC=CC=C1)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C.P(OC1=C(C=C(C=C1)C1=CC=CC=C1)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)OC1=C(C=C(C=C1)C1=CC=CC=C1)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C VVIKOPAXOBSMDD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 abstract description 5
- 239000012632 extractable Substances 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000007665 sagging Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polylactic acid composition and an additive composition thereof, wherein the additive composition comprises the following components in parts by weight based on 100 parts by weight of polylactic acid: 0.01-2 parts of main antioxidant, 0.01-2 parts of auxiliary antioxidant, 0.05-2 parts of nucleating agent A, 0.1-3 parts of nucleating agent B and 0.1-3 parts of transparent modifier. The polylactic acid composition can be made into plastic products for food packaging. The polylactic acid composition has higher transparency than pure polylactic acid, has more excellent high-temperature stability and dimensional stability, and can be used in a higher-temperature environment. The polylactic acid composition meets the requirements, has low extractables, and plastic products have lower precipitation migration performance, thereby having higher safety and sanitation performance.
Description
Technical Field
The invention belongs to the technical field of plastics, and particularly relates to a polylactic acid composition, an additive composition thereof, a plastic product and a preparation method thereof.
Background
The polylactic acid as a biodegradable low-energy-consumption high-molecular polymer has excellent biocompatibility and biodegradability and meets the FDA food contact requirement. Has positive effect on solving the problem of white pollution which puzzles the sustainable development of national economy for a long time. Polylactic acid is also a completely biodegradable polymer material, and various physical and mechanical properties of the polylactic acid are closest to those of the traditional packaging plastic.
However, pure polylactic acid has some obvious disadvantages when used as a material:
firstly, the crystallinity is low, which results in too low a heat-resistant temperature, and the product is easy to deform or block.
Secondly, the crystallization rate is too slow, the crystallinity is low, and the molding cycle is too long.
Thirdly, the heat-resistant product needs to be processed by adopting a hot die, and the temperature of the die is high.
Fourthly, high flow ratio injection molding cannot be realized, the product thickness is large, and the transparency is poor
To expand the application field of polylactic acid, it is necessary to improve physical properties and processability by modification. Particularly, the crystallinity and the crystallization rate of the polylactic acid are improved through modification, and the forming efficiency is accelerated.
The core of polylactic acid modification lies in how to effectively improve the crystallinity and the crystallization rate, but the current commercialized polylactic acid nucleating agent can improve the crystallization rate, improve the crystallinity, improve the molding efficiency, but also increase the nucleating agent, which leads to the formation of large spherulites, obviously increase the haze of the product and reduce the transparency.
Disclosure of Invention
In view of this, a polylactic acid composition, an additive composition thereof, a plastic product and a preparation method thereof are provided, which can significantly increase the crystallization rate of polylactic acid, increase the crystallinity, shorten the molding cycle of the polylactic acid product, and further improve the transparency of the polylactic acid.
An additive composition for polylactic acid comprises the following components in parts by weight based on 100 parts by weight of polylactic acid:
0.01 to 2 portions of main antioxidant,
0.01 to 2 portions of auxiliary antioxidant,
0.05 to 2 portions of nucleating agent A,
0.1 to 3 portions of nucleating agent B,
0.1 to 3 portions of transparent modifier,
the transparent modifier is ethylene oxide propylene oxide copolymer and/or polyoxyethylene,
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3, 3-bis- (4-hydroxy-3-tert-butylphenyl)) butyric acid glycol ester, triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and, At least one of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid,
the auxiliary antioxidant is at least one of tris [2, 4-di-tert-butylphenyl ] phosphite, tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenylene) bisphosphonite, bis (2, 4-dicumyl) pentaerythritol diphosphite, 3, 9-dioctadecyloxy-2, 4,8, 10-tetraoxy-3, 9-diphosphospiro [5.5] undecane, and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
Preferably, the polylactic acid is high-light pure polylactic acid, and the isotacticity is more than or equal to 98.5%.
Preferably, the weight parts of the main antioxidant are 0.01-2 parts, the weight parts of the auxiliary antioxidant are 0.01-0.5 part, the weight parts of the nucleating agent are 0.05-2 parts, the weight parts of the transparent modifier are 0.1-2 parts, and the transparent modifier is an ethylene oxide propylene oxide copolymer.
Preferably, the primary antioxidant and the secondary antioxidant are one of the following combinations:
(1) the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, and the auxiliary antioxidant is tri [2, 4-di-tert-butylphenyl ] phosphite;
(2) the main antioxidant is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the auxiliary antioxidant is tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenylyl) diphosphonite;
(3) the main antioxidant is 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene or 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and the auxiliary antioxidant is bis (2, 4-dicumyl) pentaerythritol diphosphite or bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite;
(4) the primary antioxidant is bis (3, 3-bis) (4-hydroxy-3-tert-butylphenyl)) ethylene glycol butyrate, triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate or 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, and the secondary antioxidant is 3, 9-dioctadecyloxy-2, 4,8, 10-tetraoxy-3, 9-diphosphospiro [5.5] undecane or tetrakis (2, 4-di-tert-butylphenyl-4, 4' biphenyl) diphosphonite.
Preferably, the nucleating agent A and the nucleating agent B are respectively selected from zinc phenylphosphonate, ethylene bis stearamide, malonic acid dibenzoyl hydrazine, sebacic acid dibenzoyl hydrazine, adipic acid diphenyl dihydrazide, dimethyl 1, 3-phthalate-5-sulfonic acid potassium salt, tricyclohexyl-1, 3, 5-triphenylamide, poly (D-lactic acid) PDLA, 2' -methylenebis (4, 6-di-tert-butylphenoxy) aluminum phosphate salt, calcium (1R,2S) -rel-1, 2-cyclohexanedicarboxylate, (1R,2R,3S,4S) -rel-bicyclo [2.2.1] hepta-2, 3-dicarboxylic acid disodium salt, 1,2, 3-trideoxy-4, 6: 5, 7-bis-O- [ (4-propylphenyl) methylene ] -nonanol, 1,3:2, 4-bis (3, 4-dimethylbenzylidene) -D-sorbol.
Preferably, the total weight part of the nucleating agent A and the nucleating agent B is 0.5 plus or minus 0.1 part, and the weight part of the transparent modifier is 0.5 to 1 part.
Preferably, the transparent modifier is an ethylene oxide propylene oxide copolymer.
A polylactic acid composition comprises a polylactic acid substrate and the additive composition for polylactic acid, wherein the polylactic acid substrate is preferably a high-gloss pure polylactic acid polymer.
A plastic product for food packaging, which comprises the polylactic acid composition as described above and is prepared by thermoforming or injection molding.
And, a method for preparing a plastic product for food packaging, comprising the steps of:
mixing the polylactic acid substrate and the additive composition for polylactic acid, adding the mixture into a kneader, stirring and mixing for a preset time, and discharging;
mixing and granulating the discharged materials in a double-screw extruder, and then performing injection molding or thermal molding to obtain a plastic product, wherein the molding temperature is 50-120 ℃.
The polylactic acid composition and the additive composition thereof have excellent transparency and heat resistance, have higher transparency than pure polylactic acid, and have more excellent high-temperature stability and dimensional stability. Because the nucleating agent has the characteristics of high transparency, low precipitation and the like, the defects of reduced transparency, insufficient heat resistance and the like of the current nucleating agent modified polylactic acid material can be overcome. The polylactic acid composition and the plastic product for food packaging obtained by the additive composition for polylactic acid have high transparency and good heat resistance, so that the plastic product can be conveniently used in a higher-temperature environment, such as containing high-temperature liquid or needing high-temperature sterilization before packaging, and higher rigidity and heat deformation resistance are provided for the polylactic acid and the composition thereof. The polylactic acid composition provided by the embodiment of the invention meets the requirements, and has low extractables, and the plastic product has lower precipitation migration performance, so that the polylactic acid composition has higher safety and sanitation performance.
Detailed Description
The additive composition for polylactic acid provided by the embodiment of the invention comprises the following components in parts by weight based on 100 parts by weight of polylactic acid:
0.01 to 2 portions of main antioxidant,
0.01 to 2 portions of auxiliary antioxidant,
0.05 to 2 portions of nucleating agent A,
0.1 to 3 portions of nucleating agent B,
0.1 to 3 portions of transparent modifier,
the transparent modifier is ethylene oxide propylene oxide copolymer and/or polyoxyethylene,
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3, 3-bis- (4-hydroxy-3-tert-butylphenyl)) butyric acid glycol ester, triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and, At least one of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid,
the auxiliary antioxidant is at least one of tris [2, 4-di-tert-butylphenyl ] phosphite, tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenylene) bisphosphonite, bis (2, 4-dicumyl) pentaerythritol diphosphite, 3, 9-dioctadecyloxy-2, 4,8, 10-tetraoxy-3, 9-diphosphospiro [5.5] undecane, and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
In a preferred embodiment, the polylactic acid is high-light pure polylactic acid, and the isotacticity is more than or equal to 98.5%. The optical purity of the high-gloss pure polylactic acid, namely the polylactic acid, is more than 99.5 percent. Preferably, the weight portion of the main antioxidant is 0.01-2, more preferably 0.1-0.5. The weight portion of the auxiliary antioxidant is 0.01-0.5 portion, and more preferably 0.1-0.5 portion. The nucleating agent is preferably 0.05-2 parts by weight, the transparent modifier is preferably 0.1-2 parts by weight, and the transparent modifier is ethylene oxide-propylene oxide copolymer. More preferably, the total weight of the nucleating agent A and the nucleating agent B is 0.5 plus or minus 0.1 part, the content of the nucleating agent is too high, the crystallization is faster, the crystal grains are easy to enlarge, and the improvement of the transparency is not facilitated, therefore, the optimal amount of the nucleating agent A and the nucleating agent B is 0.5 part. The transparent modifier is 0.5-1.5 parts by weight, and the transparent modifier exceeding 1.5 parts (based on 100 parts of polylactic acid) does not bring higher transparency, i.e. the transparency is not improved obviously when exceeding 1.5 parts. The nucleating agent A and the nucleating agent B can be the same or different nucleating agents.
Preferably, the primary antioxidant and the secondary antioxidant are one of the following combinations:
(1) the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol (antioxidant 1010), and the auxiliary antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168); and this is the best choice;
(2) the main antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (antioxidant 1076), and the auxiliary antioxidant is tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenyl) bisphosphonite (antioxidant P-EPQ);
(3) the main antioxidant is 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (antioxidant 330) or 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and the auxiliary antioxidant is bis (2, 4-dicumyl) pentaerythritol diphosphite (antioxidant S9228) or bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626);
(4) the primary antioxidant is bis (3, 3-bis) (4-hydroxy-3-tert-butylphenyl)) ethylene glycol butyrate, triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (antioxidant XH-245) or 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, and the secondary antioxidant is 3, 9-dioctadecyloxy-2, 4,8, 10-tetraoxy-3, 9-diphosphospiro [5.5] undecane (antioxidant 619) or tetrakis (2, 4-di-tert-butylphenyl-4, 4' biphenyl) diphosphonite (antioxidant P-EPQ).
In a specific application, the nucleating agent A and the nucleating agent B are respectively selected from zinc phenylphosphonate, ethylene bis stearamide, malonic acid dibenzoyl hydrazine, sebacic acid dibenzoyl hydrazine, adipic acid diphenyl dihydrazide, 1, 3-phthalic acid dimethyl ester-5-sulfonic acid potassium salt, tricyclohexyl-1, 3, 5-triphenylamide, poly (D-lactic acid) PDLA, 2' -methylenebis (4, 6-di-tert-butylphenoxy) aluminum phosphate salt, calcium (1R,2S) -rel-1, 2-cyclohexane dicarboxylate, (1R,2R,3S,4S) -rel-bicyclo [2.2.1] hepta-2, 3-dicarboxylic acid disodium salt, 1,2, 3-trideoxy-4, 6: 5, 7-bis-O- [ (4-propylphenyl) methylene ] -nonanol, 1,3:2, 4-bis (3, 4-dimethylbenzylidene) -D-sorbol. Preferably, the nucleating agent is zinc phenylphosphonate or adipic acid diphenyldihydrazide, and experiments prove that the adipic acid diphenyldihydrazide is optimally selected and contained in an amount of 0.5 part (calculated according to 100 parts of polylactic acid).
Preferably, the transparent modifier is an ethylene oxide propylene oxide copolymer, i.e., an EO-PO copolymer.
In another embodiment of the present invention, a polylactic acid composition is provided, which includes a polylactic acid substrate and the additive composition for polylactic acid as described above, where the polylactic acid substrate is preferably a high-gloss pure polylactic acid polymer, and the additive composition for polylactic acid adopts the above formulation and content ratio thereof. Specifically, the polylactic acid composition comprises the following components in parts by weight:
100 parts of polylactic acid, namely 100 parts of polylactic acid,
0.01 to 0.2 percent of main antioxidant,
0.01 to 0.2 percent of auxiliary antioxidant,
0.05 to 2 percent of nucleating agent,
the transparent modifier accounts for 0.1 to 3 percent of the total weight of the glass.
In another aspect, the present invention also provides a plastic product for food packaging, which is prepared from the polylactic acid composition as described above by thermoforming or injection molding. In another aspect, the present invention provides a method for preparing a plastic product for food packaging, including the following steps:
mixing a polylactic acid substrate and the additive composition for polylactic acid, adding the mixture into a kneader, stirring and mixing for a preset time, and discharging for 5-10 minutes;
mixing and granulating the discharged materials in a double-screw extruder, and then performing injection molding or thermal molding to obtain a plastic product, wherein the molding temperature is 50-120 ℃.
The additive composition for polylactic acid has excellent transparency and heat resistance, higher transparency than pure polylactic acid, and more excellent high temperature stability and dimensional stability. Because the nucleating agent has the characteristics of high transparency, low precipitation and the like, the defects of reduced transparency, insufficient heat resistance and the like of the current nucleating agent modified polylactic acid material can be overcome. The polylactic acid composition and the plastic product for food packaging obtained by the additive composition for polylactic acid have high transparency and good heat resistance, are convenient for the plastic product to be used in higher-temperature environments, such as containing high-temperature liquid or needing high-temperature sterilization before packaging, and provide higher rigidity and heat deformation resistance for the polylactic acid and the composition thereof. The polylactic acid composition provided by the embodiment of the invention meets the requirements, and has low extractables, and the plastic product has lower precipitation migration performance, so that the polylactic acid composition has higher safety and sanitation performance.
The composition, the preparation method, and the performance of the additive composition for polylactic acid will be described below with reference to a number of examples.
Example 1
The polylactic acid material is used as a base material, and the polylactic acid material comprises the following components in parts by weight:
polylactic acid material: 2000 parts of (a) by weight of the total weight,
main antioxidant: 2 parts of (a) to (b),
auxiliary antioxidant: 2 parts of (a) to (b),
nucleating agent zinc phenylphosphonate: 10 parts of (a) to (b),
EO-PO copolymer: 30 parts of.
During preparation, the components are added into a high-speed kneader, stirred, mixed and discharged for 5 minutes, mixed and granulated in a double-screw extruder, and then the polylactic resin particles are respectively injected and molded into standard sample strips for testing.
Example 2
The polylactic acid material is used as a base material, and the polylactic acid material comprises the following components in parts by weight:
polylactic acid material: 2000 parts of (a) by weight of the total weight,
main antioxidant: 2 parts of (a) to (b),
auxiliary antioxidant: 2 parts of (a) to (b),
nucleating agent diphenyl dihydrazide adipate: 10 parts of (a) to (b),
EO-PO copolymer: 30 parts of.
During preparation, the components are added into a high-speed kneader, stirred, mixed and discharged for 5 minutes, mixed and granulated in a double-screw extruder, and then the polylactic resin particles are respectively injected and molded into standard sample strips for testing.
Example 3
The polylactic acid material is used as a base material, and the polylactic acid material comprises the following components in parts by weight:
polylactic acid material: 2000 parts of (a) by weight of the total weight,
main antioxidant: 2 parts of (a) to (b),
auxiliary antioxidant: 2 parts of (a) to (b),
nucleating agent diphenyl dihydrazide adipate: 10 parts of (a) to (b),
EO-PO copolymer: 50 parts of the raw materials.
During preparation, the components are added into a high-speed kneader, stirred, mixed and discharged for 5 minutes, mixed and granulated in a double-screw extruder, and then the polylactic resin particles are respectively injected and molded into standard sample strips for testing.
Meanwhile, injection-molded standard bars as comparative examples and injection-molded standard bars as comparative examples were prepared in the formulation as shown in Table 1 below, and the test was conducted to obtain the results as shown in Table 1 below.
Test method
Testing the transparency of the injection molding sheet: the granulated polylactic acid particles are injected into sheets with the thickness of 1.0mm and 2.0mm, then the haze value of the sheets is measured,
and (5) carrying out temperature resistance test on the injection molding tensile standard sample strip.
Referring to table 1, table 1 shows a plurality of comparative examples and examples, corresponding polylactic acid resin pellet standard bars were prepared according to the above-mentioned methods and compositions of the comparative examples and examples, and the test results are shown in table 1.
| Components | Comparative example No. 1# | Comparative example No. 2# | Comparative example No. 3# | Example 1# | Example 2# | Example 3# | Comparative example 4# |
| Polylactic acid PLA-175 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 |
| Antioxidant 1010 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Antioxidant 168 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Zinc phenylphosphonate | 10 | 10 | |||||
| Adipic acid diphenyl dihydrazide | 10 | 10 | 10 | 20 | |||
| EO-PO copolymer | 30 | 30 | 50 | 100 | |||
| Injection mould temperature (115 ℃ C.) | Severe mucosa | Slightly deformed | Slightly deformed | Easy demoulding | Easy demoulding | Easy demoulding | Easy demoulding |
| Haze of 1mm sheet (%) | 15.9 | 77.34 | 58.9 | 21.2 | 14.3 | 12.6 | 29.18 |
| Haze (%) of 2mm sheet | 24.83 | 90.3 | 79.33 | 36.12 | 22.5 | 21.1 | 45.41 |
| Heat distortion temperature (. degree. C.) | 49.5 | 65.2 | 67.3 | 74．2 | 75.7 | 76.4 | 76.9 |
| Tensile sample bar 110 ℃ oven | Severe sagging | Slightly drooping | Slightly drooping | Does not droop | Does not droop | Does not droop | Does not droop |
| Soaking 1mm piece in 80 deg.C hot water | Severe deformation | Warp deformation | Warp deformation | Is not deformed | Is not deformed | Is not deformed | Is not deformed |
| Injection mould temperature (55 degree) | |||||||
| Haze of 1mm sheet (%) | 6.52 | 47.74 | 27.69 | 14.8 | 5.09 | 4.35 | 12.12 |
| Haze (%) of 2mm sheet | 14.36 | 65.69 | 42.4 | 23.6 | 8.01 | 7.1 | 21.84 |
| Heat resistance, tensile bar 110 ℃ oven | Severe sagging | Severe sagging | Severe sagging | Slight sag | Slight sag | Slight sag | Slight sag |
| Heat resistance, 1mm piece soaked in 80 deg.C hot water | Severe deformation | Severe deformation | Severe deformation | Minimal warpage | Minimal warpage | Minimal warpage | Minimal warpage |
As can be seen from the examples and comparative examples, the inventive examples have higher heat distortion temperature resistance than the polylactic acid of comparative examples 1 to 3, but have lower haze and more excellent optical properties. From the test results of the above examples, it can be seen that the haze of the standard sample of the polylactic acid resin particles of the examples of the present invention can reach 4. 35% or even less. The haze of examples 1-3 may range from 12% to 21% at an injection mold temperature of 115 ℃, and from 4% to 15% at an injection mold temperature of 55 ℃.
Claims (10)
1. The additive composition for polylactic acid is characterized by comprising the following components in parts by weight based on 100 parts by weight of polylactic acid:
0.01 to 2 portions of main antioxidant,
0.01 to 2 portions of auxiliary antioxidant,
0.05 to 2 portions of nucleating agent A,
0.1 to 3 portions of nucleating agent B,
0.1 to 3 portions of transparent modifier,
the transparent modifier is ethylene oxide propylene oxide copolymer and/or polyoxyethylene,
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3, 3-bis- (4-hydroxy-3-tert-butylphenyl)) butyric acid glycol ester, triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and, At least one of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid,
the auxiliary antioxidant is at least one of tris [2, 4-di-tert-butylphenyl ] phosphite, tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenylene) bisphosphonite, bis (2, 4-dicumyl) pentaerythritol diphosphite, 3, 9-dioctadecyloxy-2, 4,8, 10-tetraoxy-3, 9-diphosphospiro [5.5] undecane, and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
2. The additive composition for polylactic acid according to claim 1, wherein the polylactic acid is a high-gloss pure polylactic acid having an isotacticity of 98.5% or more.
3. The additive composition for polylactic acid according to claim 2, wherein the weight portion of the primary antioxidant is 0.01 to 2, the weight portion of the secondary antioxidant is 0.01 to 0.5, the weight portion of the nucleating agent is 0.05 to 2, the weight portion of the transparent modifier is 0.1 to 2, and the transparent modifier is an ethylene oxide propylene oxide copolymer.
4. The additive composition for polylactic acid according to claim 1, wherein said primary antioxidant and secondary antioxidant are one of the following combinations:
(1) the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, and the auxiliary antioxidant is tri [2, 4-di-tert-butylphenyl ] phosphite;
(2) the main antioxidant is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the auxiliary antioxidant is tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenylyl) diphosphonite;
(3) the main antioxidant is 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene or 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and the auxiliary antioxidant is bis (2, 4-dicumyl) pentaerythritol diphosphite or bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite;
(4) the primary antioxidant is bis (3, 3-bis) (4-hydroxy-3-tert-butylphenyl)) ethylene glycol butyrate, triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate or 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, and the secondary antioxidant is 3, 9-dioctadecyloxy-2, 4,8, 10-tetraoxy-3, 9-diphosphospiro [5.5] undecane or tetrakis (2, 4-di-tert-butylphenyl-4, 4' biphenyl) diphosphonite.
5. The additive composition for polylactic acid according to claim 1, the nucleating agent A and the nucleating agent B are respectively selected from zinc phenylphosphonate, ethylene bis stearamide, dibenzoyl hydrazine malonate, dibenzoyl hydrazine sebacate, diphenyl dihydrazide adipate, dimethyl 1, 3-phthalate-5-sulfonic acid potassium salt, tricyclohexyl-1, 3, 5-triphenylamide, poly (D-lactic acid) PDLA, 2' -methylenebis (4, 6-di-tert-butylphenoxy) aluminum phosphate salt, (1R,2S) -rel-1, 2-cyclohexanedicarboxylic acid calcium salt, (1R,2R,3S,4S) -rel-bicyclo [2.2.1] hepta-2, 3-dicarboxylic acid disodium salt, 1,2, 3-trideoxy-4, 6: 5, 7-bis-O- [ (4-propylphenyl) methylene ] -nonanol, 1,3:2, 4-bis (3, 4-dimethylbenzylidene) -D-sorbol.
6. The additive composition for polylactic acid according to claim 1, wherein the total weight part of the nucleating agent A and the nucleating agent B is 0.5 ± 0.1 part, and the weight part of the transparent modifier is 0.5 to 1 part.
7. The additive composition for polylactic acid according to claim 1, wherein said transparency modifier is an ethylene oxide-propylene oxide copolymer.
8. A polylactic acid composition comprising a polylactic acid substrate, preferably a high light purity polylactic acid polymer, and the additive composition for polylactic acid according to any one of claims 1 to 7.
9. A plastic product for food packaging, which is produced from the polylactic acid composition according to claim 8 by thermoforming or injection molding.
10. A preparation method of a plastic product for food packaging is characterized by comprising the following steps:
mixing a polylactic acid substrate and the additive composition for polylactic acid according to any one of claims 1 to 7, adding the mixture into a kneader, stirring and mixing for a predetermined time, and discharging;
mixing and granulating the discharged materials in a double-screw extruder, and then performing injection molding or thermal molding to obtain a plastic product, wherein the molding temperature is 50-120 ℃.
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Application publication date: 20211022 |