CN117986821A - Polymer composition, packaging material and application - Google Patents
Polymer composition, packaging material and application Download PDFInfo
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- CN117986821A CN117986821A CN202311752651.1A CN202311752651A CN117986821A CN 117986821 A CN117986821 A CN 117986821A CN 202311752651 A CN202311752651 A CN 202311752651A CN 117986821 A CN117986821 A CN 117986821A
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000005022 packaging material Substances 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 239000004626 polylactic acid Substances 0.000 claims abstract description 43
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 20
- 239000011256 inorganic filler Substances 0.000 claims abstract description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 19
- 229920002635 polyurethane Polymers 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 34
- 239000007822 coupling agent Substances 0.000 claims description 22
- 239000002667 nucleating agent Substances 0.000 claims description 21
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- -1 alum Chemical compound 0.000 claims description 13
- 239000004970 Chain extender Substances 0.000 claims description 12
- 239000004014 plasticizer Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 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 11
- 239000000314 lubricant Substances 0.000 claims description 11
- 239000000454 talc Substances 0.000 claims description 11
- 235000012222 talc Nutrition 0.000 claims description 11
- 229910052623 talc Inorganic materials 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 230000000655 anti-hydrolysis Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 150000001718 carbodiimides Chemical class 0.000 claims description 7
- YLWQQYRYYZPZLJ-UHFFFAOYSA-N 12-hydroxy-n-[2-(12-hydroxyoctadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC(O)CCCCCC YLWQQYRYYZPZLJ-UHFFFAOYSA-N 0.000 claims description 6
- 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 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
- 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 claims description 6
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- 229920001992 poloxamer 407 Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 239000002253 acid Substances 0.000 claims description 4
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- 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
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-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
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- 239000012948 isocyanate Chemical class 0.000 claims description 3
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- 239000004593 Epoxy Chemical class 0.000 claims description 2
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019496 Pine nut oil Nutrition 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 229940037003 alum Drugs 0.000 claims description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 2
- MDKXFHZSHLHFLN-UHFFFAOYSA-N alumanylidynecobalt Chemical compound [Al].[Co] MDKXFHZSHLHFLN-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 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
- 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
- 239000003814 drug Substances 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
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229960001679 octinoxate Drugs 0.000 claims description 2
- PFYOXQQFOSJVRA-UHFFFAOYSA-N octyl 2-(dimethylamino)benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1N(C)C PFYOXQQFOSJVRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 2
- 229960001173 oxybenzone Drugs 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000010490 pine nut oil Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 2
- 239000002537 cosmetic Substances 0.000 claims 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 claims 2
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 229940079593 drug Drugs 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
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- 239000004698 Polyethylene Substances 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 244000005700 microbiome Species 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
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- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
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- 229920001875 Ebonite Polymers 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 206010057249 Phagocytosis Diseases 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polymer composition which comprises polylactic acid PLA, carbon dioxide-based polyurethane PPC-TPU and an inorganic filler. The invention also provides a degradable material prepared by using the polymer composition. The degradable material can be applied to the field of packaging materials.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high polymer composition, a packaging material and application.
Background
The packaging materials in daily life, such as daily chemical product packaging bottles and the like, are mainly made of polyolefin materials such as polyethylene or polypropylene, and have the advantages of corrosion resistance, low cost, light weight, diversified shapes and portability, but the polyethylene or polypropylene materials have the defects of low recovery rate and little degradation in natural environment, and can form ecological hazard and environmental disaster of microplastic after fragmentation.
The completely degradable material refers to the polymer material is hydrolyzed or hydrolyzed into low molecular substances by utilizing temperature, humidity, minerals and microorganisms (such as bacteria, fungi, algae and the like) in the environment, and then the low molecular substances are completely decomposed into water, carbon dioxide and biomass by phagocytosis of the microorganisms. The bio-polyester such as PLA, PBS, PBSA, PBAT, PCL, PHA, PHBV widely used at present has the characteristics of being processable, strong in environment and easy to degrade, and can be used as a potential packaging material for packaging daily chemical products.
Polylactic acid (PLA) is a typical aliphatic polyester, the basic structural unit of which is lactic acid (2-hydroxy propionic acid), is a completely degradable material with pure bio-base as a raw material, but is brittle and fragile, lacks elasticity and flexibility, and limits the application of the polylactic acid to a great extent. Therefore, there is a need to develop more high-toughness polylactic acid materials to promote the popularization and application thereof in the field of packaging materials.
Disclosure of Invention
In order to solve one of the above technical problems in the prior art, the present invention provides a polymer composition and a degradable packaging material prepared by using the polymer composition.
In a first aspect, the present invention provides a polymeric composition comprising polylactic acid PLA, carbon dioxide based polyurethane PPC-TPU, and an inorganic filler.
The application relates to a carbon dioxide-based polyurethane or PPC-TPU or carbon dioxide-based polyurethane PPC-TPU, which is a compound of carbon dioxide-based polyol PPC (polypropylene carbonate) and thermoplastic polyurethane elastomer, and is a novel biodegradable polymer material prepared by taking carbon dioxide and propylene oxide as raw materials, preparing PPC polyol through polymerization reaction, and then carrying out polymerization reaction on the PPC polyol and isocyanate. The application discovers that the carbon dioxide-based polyurethane PPC-TPU is used as the plasticizer, so that the polylactic acid material has excellent elongation at break and tearing strength, the toughness is enhanced, the barrier property to oxygen and water vapor is improved, the acid and alkali resistance is improved, the transparency is high, the shelf life is prolonged, and the biodegradable material can be composted.
In some embodiments, the polymeric composition comprises, by weight: 60-90 parts of polylactic acid, 8-20 parts of PPC-TPU and 5-20 parts of inorganic filler.
In the polymer composition of the present invention, the mass fraction of polylactic acid may be 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, 85 parts, 88 parts, 90 parts or any value therebetween.
In the polymer composition of the present invention, the mass parts of the PPC-TPU may be 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts or any value therebetween.
In the polymer composition of the present invention, the mass fraction of the inorganic filler may be 5 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts or any value therebetween.
In some preferred embodiments, the polymeric composition comprises, by weight: 68-72 parts of polylactic acid PLA, 14-18 parts of carbon dioxide-based polyurethane PPC-TPU and 5-15 parts of inorganic filler.
In some embodiments, the inorganic filler comprises talc. In some preferred embodiments, the talc is a talc modified with a coupling agent, the coupling agent including at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a cobaltate coupling agent, an aluminum-titanium composite coupling agent, and an aluminum-cobalt composite coupling agent. In some preferred embodiments, the coupling agent comprises an organosilane coupling agent JL-G06FL. Preferably, the amount of the coupling agent added to the talc is 0.5 to 2% by mass of the talc, and may be, for example, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2% or any value therebetween. In some embodiments, the method of modifying talc comprises the steps of:
Adding talcum powder into a high-speed mixer, heating to 100-110 ℃, adding a coupling agent, and stirring for 10-15 minutes at 100-130 ℃ and 1400-1600 rp. Preferably, the coupling agent is added to the talc by spraying or by dripping.
In some embodiments, the polymeric composition further comprises an adjuvant. In some embodiments, the adjuvants include, but are not limited to: at least one of a lubricant, a plasticizer, a chain extender, an anti-hydrolysis agent, a nucleating agent, an antioxidant and an ultraviolet absorber. In some embodiments, the adjuvants in the polymeric composition include lubricants, plasticizers, chain extenders, anti-hydrolysis agents, nucleating agents, antioxidants, and ultraviolet absorbers. In some embodiments, the mass ratio of the lubricant, the plasticizer, the chain extender, the anti-hydrolysis agent, the nucleating agent, the antioxidant and the ultraviolet absorber is (0.5-2): (0.5-2): (0.2-2): (1-2): (0.3-6.8): (0.1-0.5): (0.1-0.8).
In the polymer composition of the present invention, the auxiliary agent may be used in an amount of 1 to 18 parts, for example, 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, etc.
In some embodiments, the polymeric composition comprises, by weight: 60-90 parts of polylactic acid, 8-20 parts of PPC-TPU, 5-20 parts of inorganic filler and 1-18 parts of auxiliary agent.
In some preferred embodiments, the polymeric composition comprises, by weight: 65-75 parts of polylactic acid, 12-20 parts of PPC-TPU, 5-15 parts of inorganic filler and 2-10 parts of auxiliary agent.
In some preferred embodiments, the polymeric composition comprises, by weight: 68-72 parts of polylactic acid, 14-18 parts of PPC-TPU, 5-15 parts of inorganic filler and 2-10 parts of auxiliary agent.
The lubricant of the present invention includes epoxidized vegetable oils including, but not limited to: 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 nut oil, epoxidized tung oil and the like. In some preferred embodiments, the lubricant comprises Epoxidized Soybean Oil (ESO).
Plasticizers of the present invention include phthalate esters, including but not limited to: dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dipentyl phthalate, and the like, including but not limited to: tri-n-butyl citrate, acetyl tributyl citrate, and the like. In some preferred embodiments, the plasticizer comprises acetyl tributyl citrate (ATBC).
Chain extenders of the present invention include, but are not limited to: ethylene maleic anhydride copolymers, styrene acrylate copolymers or copolymers of styrene, methyl methacrylate and glycidyl methacrylate, and the like. In some preferred embodiments, the chain extender comprises a copolymer of styrene, methyl methacrylate, glycidyl methacrylate (BTCE-9013).
The anti-hydrolysis agents of the present invention include, but are not limited to: monomeric carbodiimide, polymeric carbodiimide, isocyanates, oxazolines, epoxy compounds, and the like. In some preferred embodiments, the hydrolysis inhibitor comprises polymeric carbodiimide BTWR-500.
The nucleating agents of the present invention include inorganic nucleating agents including, but not limited to, inorganic nucleating agents and/or organic nucleating agents: talc, calcium carbonate, silica, alum, titanium dioxide, calcium oxide, magnesium oxide, carbon black, mica, etc., including but not limited to: fatty carboxylic acid metal compounds, sorbitol benzylidene derivatives, aromatic carboxylic acid metal compounds, organic phosphates, wood acids and derivatives thereof, sodium benzoate and bis (p-tert-butylbenzoic acid) carboxyaluminum, organic polymer nucleating agents, and the like. In some preferred embodiments, the nucleating agent comprises a mixture of ethylene bis-12-hydroxystearamide and poloxamer 407, preferably the mass ratio of ethylene bis-12-hydroxystearamide to poloxamer 407 is 1: (0.1-0.5).
The antioxidants of the present invention include a multi-component hindered phenolic antioxidant and/or a phosphite antioxidant, including but not limited to: antioxidant 1010, antioxidant 1330, antioxidant 1790, etc.; the phosphite antioxidants include, but are not limited to: antioxidant 168, antioxidant 618, antioxidant 626, antioxidant 9228, antioxidant TNPP and the like. In some preferred embodiments, the antioxidant comprises a mixture of antioxidant 1010 and antioxidant 168, preferably the antioxidant 1010 and antioxidant 168 are present in a mass ratio of 1: (1.5 to 2.5), for example, 1:2.
The ultraviolet light absorber of the present invention includes, but is not limited to, octyl methoxycinnamate, 4-benzophenone, oxybenzone, octyl dimethylaminobenzoate, hindered amine ultraviolet light absorbers, and the like. In some preferred embodiments, the ultraviolet light absorber comprises a hindered amine ultraviolet light absorber UV-783.
In some embodiments, the polymeric composition comprises, by weight:
In some preferred embodiments, the polymeric composition comprises, by weight:
in some more preferred embodiments, the polymeric composition comprises, by weight:
in a second aspect, the present invention provides a degradable packaging material, the preparation raw materials of which comprise the polymer composition according to the first aspect.
The packaging material of the present invention includes, but is not limited to, food packaging materials, pharmaceutical packaging materials, cosmetic packaging materials, daily necessities packaging materials, and the like.
In a third aspect, the present invention provides a method of preparing a degradable packaging material according to the second aspect of the invention, comprising the steps of:
(1) Mixing raw materials comprising polylactic acid PLA, carbon dioxide-based polyurethane PPC-TPU, an inorganic filler and optional auxiliary agents in proportion to obtain a mixture;
(2) Mixing and granulating the mixture in a double-screw extruder to obtain an extruded material;
(3) The extrusion material is melted and molded to obtain the degradable packaging material.
In some embodiments, in step (1), the mixing is performed at a speed of 1000 to 1500 rpm.
In some embodiments, the twin screw extruder of step (2) is operated at a temperature of 150 to 200℃and at a speed of 300 to 400rpm.
In some embodiments, step (2) comprises: transferring the mixture into a double-screw extruder, mixing, melting, extruding, cooling and granulating by the double-screw extruder to obtain an extruded material, wherein the double-screw extruder comprises 10 areas, the temperature of each area is 155-160 ℃, 170-180 ℃, 175-185 ℃, 180-190 ℃, 190-200 ℃, 185-190 ℃, the feeding amount of the screw is 5-15 kg/h, the rotating speed of the screw is 300-400 rpm, and the particle size of the extruded material after granulating is 2-3 mm.
In a fourth aspect, the present invention provides the use of a polymeric composition according to the first aspect for the preparation of a degradable packaging material.
The packaging materials of the present invention include, but are not limited to: food packaging materials, medicine packaging materials, cosmetic packaging materials, daily necessities packaging materials, and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. The invention combines the carbon dioxide-based polyurethane PPC-TPU and the polylactic acid PLA to obtain the biological base material with degradability and high toughness, and can improve the barrier property of the polylactic acid to oxygen and water vapor and the acid and alkali resistance, thereby being applicable to various packaging materials.
2. The composition can also be used for preparing polylactic acid modified material particles, the manufacturing process is simple, and the masterbatch can be added according to the need in the extrusion granulation process to prepare modified materials with different colors.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. The specific embodiments described herein are for purposes of illustration only and are not to be construed as limiting the invention in any way.
The raw materials used in the present invention are all commercially available, unless otherwise specified.
The following examples and comparative examples of the present invention were prepared from the following raw materials in the form of their sources:
Polylactic acid: purchased from Anhui Feng Yuanfu Talai polylactic acid Co., ltd., brand FY801.
Carbon dioxide based polyurethane (PPC-TPU) purchased from Jiangsu middle-family Jinlong environmental protection New materials Co., ltd, wherein the PPC-TPU brand used in examples 1 to 6, examples 8 to 9 and comparative examples 2 to 4 is T9, and the PPC-TPU brand used in example 7 is T4.
The preparation process of the modified talcum powder comprises the following steps:
Adding talcum powder into a high-speed mixer, stirring and preheating to 105 ℃, then adding an organosilane coupling agent accounting for 1.5% of the mass of the talcum powder in a spraying or dripping mode, mixing for 10-15 minutes, and maintaining the rotating speed of the high-speed mixer at 1500rpm and the temperature at 100-130 ℃. The talcum powder is purchased from sea city New Guangdong powder material limited company, 8000 meshes and food grade; the organosilane coupling agent is purchased from Nanjing Jinlaiwang New Material technologies Co., ltd., brand JL-G06FL.
Chain extender: copolymers of styrene, methyl methacrylate and glycidyl methacrylate, purchased from Nanjing Baitong New Material Co., ltd., trade name BTCE-9013.
Hydrolysis inhibitor: polymeric carbodiimide purchased from Nanjing Baitong New Material Co., ltd., trade mark BTWR-500;
an antioxidant: antioxidant 1010 and antioxidant 168 in a mass ratio of 1:2, purchased from basf;
Ultraviolet absorber: basoff' s 783；
Nucleating agent: ethylene bis-12-hydroxystearamide (EBH) and Poloxamer (Poloxamer) 407 in a mass ratio of 8: 3.
Example 1-example 9
Examples 1 to 9 provide polylactic acid modified materials, the raw material formulation (parts by mass) of which is shown in Table 1.
TABLE 1
The polylactic acid modified materials described in examples 1 to 9 were prepared as follows:
First, base material particles are prepared
Polylactic acid (PLA), carbon dioxide-based polyurethane (PPC-TPU), inorganic filler modified talcum powder, lubricant ESO, plasticizer ATBC, chain extender BTCE-9013, antioxidant, ultraviolet absorbent, anti-hydrolysis agent and nucleating agent are added into a high-speed mixer according to the proportion in Table 1, and are uniformly stirred to obtain the mixture.
Second, blending granulation
Transferring the uniformly stirred mixture into a double-screw extruder, mixing, melting, extruding, cooling and granulating the mixture by the double-screw extruder to obtain extruded materials, wherein the temperature of each region is 155-160 ℃, 170-180 ℃, 175-185 ℃, 180-190 ℃, 190-200 ℃, 185-190 ℃, the feeding amount of the screw is 10kg/h, the rotating speed of the screw is 360rpm, and the speed of the granulator is adjusted to enable the particle size to be 2-3 mm.
Third step, vacuum drying
And (3) drying the extruded material in a vacuum dryer in a vacuum drying mode, wherein the vacuum degree is-0.09 to-0.1 MPa, the drying temperature is 70-90 ℃, the drying time is 4-6 hours, and the polylactic acid modified material is obtained after the water content is less than 500 ppm.
Comparative example 1
The difference from example 6 is that no PPC-TPU is added.
Comparative example 2
The difference from example 6 is that the "PPC-TPU" is replaced by a common "TPU".
Comparative example 3
The difference from example 6 is that the inorganic filler used is conventional talc, i.e. not modified by the process described above.
The polylactic acid modified materials prepared in each example and comparative example are prepared into sample bars by selecting a plastic mold according to GB/T9352-2008 compression molding of plastic thermoplastic material samples, and according to GB/T1043-2008 determination of impact Property of Plastic simple beams, GB/T1633-2000 determination of Vicat Softening Temperature (VST) of thermoplastic plastics, GB/T1634.2-2019 determination of deformation temperature under load of plastics, section 2: the test of the plastic and hard rubber was carried out on the sample bars, and the sample bars of each example and comparative example were subjected to a minimum of 5 tests, and the average value was taken, and the specific test results are shown in Table 2.
TABLE 2
Compared with the method in which TPU is not added in comparative example 1 and common TPU is added in comparative example 2, the method in example 6 of the application uses carbon dioxide-based polyurethane PPC-TPU, so that the impact resistance and the thermal performance of the polylactic acid material can be obviously improved.
As can be seen from the performance test data of examples 1-3 and comparative example 3, the addition of an appropriate amount of modified talc significantly increases the impact strength of the polylactic acid material.
It can be seen from the performance test data of examples 3 to 7 and example 8 that the PPC-TPU used in an amount of 20 parts by mass has a higher impact strength, but some of the thermal properties are lost compared to 16 parts by mass of PPC-TPU.
As can be seen from the performance test data of examples 8 and 9, when the content of PPC-TPU is continuously increased, i.e., the content of PPC-TPU exceeds 20 parts by mass, the modified polylactic acid material has better impact properties, but the thermal properties of the sample bars are rapidly reduced, so that the amount of PPC-TPU used needs to be controlled within a proper range.
From comparison of the results of example 7 and example 6, it can be seen that T9 used in example 6 has relatively superior impact resistance and heat resistance to T4.
The technical scheme of the invention is not limited to the specific embodiment, and all technical modifications made according to the technical scheme of the invention fall within the protection scope of the invention.
Claims (10)
1. A polymer composition comprises polylactic acid PLA, carbon dioxide based polyurethane PPC-TPU and inorganic filler.
2. The polymeric composition of claim 1, wherein the polymeric composition comprises, by weight: 60-90 parts of polylactic acid PLA, 8-20 parts of carbon dioxide-based polyurethane PPC-TPU and 5-20 parts of inorganic filler;
Preferably, the polymeric composition comprises, by weight: 68-72 parts of polylactic acid PLA, 14-18 parts of carbon dioxide-based polyurethane PPC-TPU and 5-15 parts of inorganic filler.
3. The polymer composition according to claim 1 or 2, wherein the inorganic filler comprises talc;
Preferably, the talcum powder is talcum powder modified by a coupling agent, and the coupling agent comprises at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a cobaltate coupling agent, an aluminum-titanium composite coupling agent and an aluminum-cobalt composite coupling agent;
more preferably, the addition amount of the coupling agent in the talcum powder is 0.5-2% of the mass of the talcum powder.
4. A polymeric composition according to any one of claims 1 to 3, further comprising an auxiliary agent;
preferably, the auxiliary agent comprises at least one of a lubricant, a plasticizer, a chain extender, an anti-hydrolysis agent, a nucleating agent, an antioxidant and an ultraviolet absorber; more preferably, lubricants, plasticizers, chain extenders, anti-hydrolysis agents, nucleating agents, antioxidants, and ultraviolet absorbers;
Preferably, the polymeric composition comprises, by weight: 60 to 90 parts of polylactic acid PLA, 8 to 20 parts of carbon dioxide-based polyurethane PPC-TPU, 5 to 20 parts of inorganic filler and 1 to 18 parts of auxiliary agent;
More preferably, the polymeric composition comprises, by weight: 68-72 parts of polylactic acid PLA, 14-18 parts of carbon dioxide-based polyurethane PPC-TPU, 5-15 parts of inorganic filler and 2-10 parts of auxiliary agent;
Further preferably, in the auxiliary agent, the mass ratio of the lubricant, the plasticizer, the chain extender, the anti-hydrolysis agent, the nucleating agent, the antioxidant and the ultraviolet absorber is (0.5-2): (0.5-2): (0.2-2): (1-2): (0.3-6.8): (0.1-0.5): (0.1-0.8).
5. The polymer composition according to claim 4, wherein the lubricant comprises an epoxidized vegetable oil, preferably at least one selected from the group consisting 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 nut oil, and epoxidized tung oil; and/or the number of the groups of groups,
The plasticizer comprises phthalic acid esters or citric acid esters, wherein the phthalic acid esters preferably comprise at least one of dimethyl phthalate, diethyl phthalate, dibutyl phthalate and dipentyl phthalate, and the citric acid esters preferably comprise tri-n-butyl citrate and/or acetyl tributyl citrate; and/or the number of the groups of groups,
The chain extender comprises at least one of ethylene maleic anhydride copolymer, acrylic acid styrene copolymer or copolymer of styrene, methyl methacrylate and glycidyl methacrylate; and/or the number of the groups of groups,
The anti-hydrolysis agent comprises at least one of monomer carbodiimide, polymeric carbodiimide, isocyanate, oxazoline compounds and epoxy compounds; and/or the number of the groups of groups,
The nucleating agent comprises at least one of an inorganic nucleating agent and an organic nucleating agent, wherein the inorganic nucleating agent preferably comprises at least one of talcum powder, calcium carbonate, silicon dioxide, alum, titanium dioxide, calcium oxide, magnesium oxide, carbon black and mica, and the organic nucleating agent preferably comprises at least one of aliphatic carboxylic acid metal compound, sorbitol benzylidene derivative, aromatic carboxylic acid metal compound, organic phosphate, wood acid and derivatives thereof, sodium benzoate and bis (p-tert-butyl benzoic acid) aluminum carboxyl, and organic polymer nucleating agent; and/or the number of the groups of groups,
The antioxidant comprises a multi-element hindered phenol antioxidant and/or a phosphite antioxidant; and/or the number of the groups of groups,
The ultraviolet absorbent comprises at least one of octyl methoxycinnamate, 4-diphenyl ketone, oxybenzone, octyl dimethylaminobenzoate and hindered amine ultraviolet absorbent.
6. The polymeric composition of claim 5, wherein the lubricant comprises epoxidized soybean oil; and/or the number of the groups of groups,
The plasticizer comprises acetyl tributyl citrate; and/or the number of the groups of groups,
The chain extender comprises a copolymer of styrene, methyl methacrylate and glycidyl methacrylate; and/or the number of the groups of groups,
The anti-hydrolysis agent comprises polymerized carbodiimide; and/or the number of the groups of groups,
The nucleating agent comprises a mixture of ethylene bis-12-hydroxystearamide and poloxamer 407, preferably, the mass ratio of the ethylene bis-12-hydroxystearamide to the poloxamer 407 is 1: (0.1 to 0.5); and/or the number of the groups of groups,
The antioxidant comprises a mixture of an antioxidant 1010 and an antioxidant 168, and preferably the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1: (1.5-2.5); and/or the number of the groups of groups,
The ultraviolet light absorber includes a hindered amine ultraviolet light absorber UV-783.
7. The polymer composition according to any one of claims 1 to 6, wherein the polymer composition comprises, by weight:
preferably, the polymeric composition comprises, by weight:
8. A degradable packaging material, the raw materials for preparing which comprises the macromolecule composition of any one of claims 1-7;
preferably, the packaging material includes packaging materials for foods, medicines, cosmetics and daily necessities.
9. A method of making the degradable packaging material of claim 8, comprising the steps of:
(1) Mixing raw materials comprising polylactic acid PLA, carbon dioxide-based polyurethane PPC-TPU, an inorganic filler and optional auxiliary agents in proportion to obtain a mixture;
(2) Mixing and granulating the mixture in a double-screw extruder to obtain an extruded material;
(3) The extrusion material is melted and molded to obtain the degradable packaging material;
Preferably, in step (1), the mixing is carried out at a speed of 1000 to 1500 rpm;
Preferably, in the step (2), the processing temperature of the twin-screw extruder is 150-200 ℃; more preferably, the twin-screw extruder unit comprises 10 zones, each zone having a temperature of 155℃～160℃、170℃～180℃、175℃～185℃、180℃～190℃、190℃～200℃、190℃～200℃、190℃～200℃、190℃～200℃、190℃～200℃、185℃～190℃;
Preferably, the feeding amount of the screw of the double-screw extruder is 5-15 kg/h, the rotating speed of the screw is 300-400 rpm, and the grain diameter of the extruded material is 2-3 mm.
10. Use of a polymeric composition according to any one of claims 1 to 7 for the preparation of a degradable packaging material, preferably comprising packaging materials for food, pharmaceutical, cosmetic and commodity products.
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