CN114058076A - Rare earth nucleating agent, preparation method and application thereof, high-crystallinity modified polylactic acid film, and preparation method and application thereof - Google Patents
Rare earth nucleating agent, preparation method and application thereof, high-crystallinity modified polylactic acid film, and preparation method and application thereof Download PDFInfo
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- CN114058076A CN114058076A CN202111624465.0A CN202111624465A CN114058076A CN 114058076 A CN114058076 A CN 114058076A CN 202111624465 A CN202111624465 A CN 202111624465A CN 114058076 A CN114058076 A CN 114058076A
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- rare earth
- polylactic acid
- nucleating agent
- crystallinity
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 138
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 97
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 91
- 229920006381 polylactic acid film Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 239000004626 polylactic acid Substances 0.000 claims abstract description 72
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 65
- -1 lactic acid rare earth Chemical class 0.000 claims abstract description 56
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000004310 lactic acid Substances 0.000 claims abstract description 25
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 25
- 239000003446 ligand Substances 0.000 claims abstract description 25
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- 235000013305 food Nutrition 0.000 claims abstract description 8
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 37
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000137 annealing Methods 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 24
- 238000007731 hot pressing Methods 0.000 claims description 23
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000001540 sodium lactate Substances 0.000 claims description 22
- 229940005581 sodium lactate Drugs 0.000 claims description 22
- 235000011088 sodium lactate Nutrition 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007822 coupling agent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 229920001610 polycaprolactone Polymers 0.000 claims description 14
- 239000004632 polycaprolactone Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims description 10
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 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 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 11
- 230000008025 crystallization Effects 0.000 abstract description 11
- 230000009194 climbing Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010899 nucleation Methods 0.000 abstract description 4
- 230000006911 nucleation Effects 0.000 abstract description 4
- 239000005022 packaging material Substances 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 62
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 17
- RFEFPOFKDIOFQW-UHFFFAOYSA-K cerium(3+);2-hydroxypropanoate Chemical compound [Ce+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O RFEFPOFKDIOFQW-UHFFFAOYSA-K 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 7
- ZTOKUMPYMPKCFX-CZNUEWPDSA-N (E)-17-[(2R,3R,4S,5S,6R)-6-(acetyloxymethyl)-3-[(2S,3R,4S,5S,6R)-6-(acetyloxymethyl)-3,4,5-trihydroxyoxan-2-yl]oxy-4,5-dihydroxyoxan-2-yl]oxyoctadec-9-enoic acid Chemical compound OC(=O)CCCCCCC/C=C/CCCCCCC(C)O[C@@H]1O[C@H](COC(C)=O)[C@@H](O)[C@H](O)[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](COC(C)=O)O1 ZTOKUMPYMPKCFX-CZNUEWPDSA-N 0.000 description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 6
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003876 biosurfactant Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OMGKKRHVRFEREE-UHFFFAOYSA-K 2-hydroxypropanoate;lanthanum(3+) Chemical compound [La+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O OMGKKRHVRFEREE-UHFFFAOYSA-K 0.000 description 3
- VXDRYJKQOSTIIC-UHFFFAOYSA-K 2-hydroxypropanoate;neodymium(3+) Chemical compound [Nd+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O VXDRYJKQOSTIIC-UHFFFAOYSA-K 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical class CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- SLMWYXDNPMGINM-UHFFFAOYSA-N 2-[4-[3,5-dimethyl-1-(2-propylheptyl)pyridin-4-ylidene]-3,5-dimethylcyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound CC1=CN(CC(CCC)CCCCC)C=C(C)C1=C1C(C)=CC(=C(C#N)C#N)C=C1C SLMWYXDNPMGINM-UHFFFAOYSA-N 0.000 description 1
- 101100207005 Caenorhabditis elegans tmc-2 gene Proteins 0.000 description 1
- XGULBQUJRQPLOG-OOOULUNWSA-N O([C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)COCC=1C=CC=CC=1)CC)[C@@H]1O[C@H](C)[C@@H](O)[C@H](N(C)C)[C@H]1O Chemical compound O([C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)COCC=1C=CC=CC=1)CC)[C@@H]1O[C@H](C)[C@@H](O)[C@H](N(C)C)[C@H]1O XGULBQUJRQPLOG-OOOULUNWSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides a rare earth nucleating agent, a preparation method and application thereof, a high-crystallinity modified polylactic acid film, a preparation method and application thereof, and relates to the technical field of packaging materials. The rare earth nucleating agent provided by the invention is a lactic acid rare earth complex, the rare earth element in the rare earth nucleating agent can generate a strong coordination effect on carboxylic acid in polylactic acid, and a lactic acid ligand in the rare earth nucleating agent is a synthetic raw material of polylactic acid and has good compatibility with the polylactic acid; the rare earth nucleating agent can improve the crystallinity of the polylactic acid by a dual mechanism of heterogeneous nucleation crystallization and climbing crystallization, and has an obvious crystallization promoting effect. The invention also provides a high-crystallinity modified polylactic acid film, which has higher crystallinity and excellent comprehensive performance due to the addition of the rare earth nucleating agent; in addition, the rare earth nucleating agent, the plasticizer and the toughening agent can synergistically modify the polylactic acid, the comprehensive performance of the polylactic acid can be further improved, and the high-crystallinity modified polylactic acid film can be applied to food packaging.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to a rare earth nucleating agent, a preparation method and application thereof, a high-crystallinity modified polylactic acid film, and a preparation method and application thereof.
Background
The synthetic raw materials of the polylactic acid are derived from non-petrochemical products, can return to nature through biodegradation after being used, have the characteristic of environmental friendliness, are more and more widely used for various packaging materials, and are expected to replace part of petrochemical synthetic non-degradable polymer packaging materials.
However, polylactic acid itself has a defect of low crystallinity, and the application range is greatly limited. The defect of low crystallinity of the polylactic acid is overcome, and the most common method is to add a nucleating agent into the polylactic acid. The nucleating agent at the present stage mainly comprises an organic nucleating agent and an inorganic nucleating agent, wherein the commonly used organic nucleating agents such as Ethylene Bis Stearamide (EBS), TMC-306 and TMC-300 have the defect of easy precipitation and are not suitable for being applied in the field of food packaging; the common inorganic nucleating agents such as talcum powder, montmorillonite, calcium carbonate and zinc oxide have poor compatibility with polylactic acid, so that the polylactic acid is non-uniform in crystallization and poor in product quality.
Disclosure of Invention
In view of the above, the present invention aims to provide a rare earth nucleating agent, a preparation method and an application thereof, a high-crystallinity modified polylactic acid film, a preparation method and an application thereof. The rare earth nucleating agent provided by the invention has good compatibility with polylactic acid, is not easy to precipitate, and can improve the comprehensive performance of the polylactic acid on the basis of obviously improving the crystallinity of the polylactic acid.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a rare earth nucleating agent which is a lactic acid rare earth complex.
Preferably, the rare earth element in the lactic acid rare earth complex comprises one or more of cerium, lanthanum, neodymium and samarium.
The invention provides a preparation method of the rare earth nucleating agent in the technical scheme, which comprises the following steps:
mixing a ligand compound, a surfactant, a coupling agent and water to obtain a first solution; the ligand compound comprises lactic acid and/or sodium lactate;
dissolving a rare earth compound to obtain a second solution; the rare earth compound comprises one or more of rare earth nitrate, rare earth chloride and rare earth oxalate;
dropwise adding the second solution into the first solution to perform a coordination reaction to obtain a precipitate; and sequentially centrifuging, filtering and drying the precipitate to obtain the rare earth nucleating agent.
Preferably, the mass concentration of the ligand compound in the first solution is 55-60%; the pH value of the first solution is 6-9;
the molar ratio of the rare earth compound, the ligand compound, the surfactant and the coupling agent is 1 (0.5-9): 0.0005-0.02.
Preferably, the temperature of the coordination reaction is 30-60 ℃ and the time is 2-24 h.
The invention provides the application of the rare earth nucleating agent in the technical scheme or the rare earth nucleating agent prepared by the preparation method in the technical scheme in polylactic acid materials.
The invention provides a high-crystallinity modified polylactic acid film which comprises the following preparation raw materials in parts by mass:
57.5 to 99.5 parts of polylactic acid,
0.5-2.5 parts of rare earth nucleating agent,
0 to 20 parts of a plasticizer,
0-20 parts of a toughening agent;
the rare earth nucleating agent is the rare earth nucleating agent prepared by the technical scheme or the preparation method of the technical scheme.
Preferably, the plasticizer comprises one or more of polyethylene glycol, tributyl citrate and epoxidized soybean oil; the toughening agent comprises one or more of natural rubber, polycaprolactone and polybutylene adipate/terephthalate.
The invention provides a preparation method of a high-crystallinity modified polylactic acid film, which comprises the following steps:
carrying out melt blending on the rare earth nucleating agent, the polylactic acid, the plasticizer and the toughening agent to obtain a blend;
sequentially carrying out hot pressing and annealing on the blend to obtain the high-crystallinity modified polylactic acid film; the annealing temperature is 90-110 ℃, and the annealing time is 1-10 min.
Preferably, the melt blending is carried out in a torque rheometer; the temperature of the melt blending is 170-200 ℃, the rotating speed is 45-60 rpm, and the time is 4-10 min;
the hot pressing temperature is 165-190 ℃, the pressure is 10-15 MPa, and the time is 30-120 s.
The invention also provides the application of the high-crystallinity modified polylactic acid film in the technical scheme or the high-crystallinity modified polylactic acid film prepared by the preparation method in the technical scheme in food packaging.
The invention provides a rare earth nucleating agent which is a lactic acid rare earth complex. In the invention, the rare earth element in the rare earth nucleating agent can generate strong coordination effect on carboxylic acid in polylactic acid, and a lactic acid ligand in the rare earth nucleating agent is a synthetic raw material of the polylactic acid and has good compatibility with the polylactic acid; the rare earth nucleating agent can improve the crystallinity of the polylactic acid by a dual mechanism of heterogeneous nucleation crystallization and climbing crystallization, and has an obvious crystallization promoting effect. Therefore, the rare earth nucleating agent provided by the invention has good compatibility with polylactic acid, is not easy to precipitate, can obviously improve the crystallinity of the polylactic acid, and improves the comprehensive performance of the polylactic acid. The rare earth nucleating agent provided by the invention can be effectively applied to polylactic acid materials.
The preparation method of the rare earth nucleating agent provided by the technical scheme is simple in process, easy to operate and convenient for large-scale production.
The invention provides a high-crystallinity modified polylactic acid film which comprises the following preparation raw materials in parts by mass: 0.5-2.5 parts of rare earth nucleating agent, 57.5-99.5 parts of polylactic acid, 0-20 parts of plasticizer and 0-20 parts of toughening agent; the rare earth nucleating agent is the rare earth nucleating agent prepared by the technical scheme or the preparation method of the technical scheme. The polylactic acid film provided by the invention has higher crystallinity and excellent comprehensive performance due to the addition of the rare earth nucleating agent; in addition, the rare earth nucleating agent, the plasticizer and the toughening agent can be used for synergistically modifying the polylactic acid, so that the comprehensive performance of the polylactic acid can be further improved, and the practical application requirements can be better met. The example results show that the crystallinity of the high-crystallinity modified polylactic acid film provided by the invention can reach 52%, and the high-crystallinity modified polylactic acid film has higher tensile strength, elongation at break and impact strength.
The preparation method of the high-crystallinity modified polylactic acid film provided by the technical scheme provided by the invention has the advantages of simple process and easiness in operation, and the crystallinity of the polylactic acid can be further ensured by controlling the annealing temperature and time.
The invention provides the application of the high-crystallinity modified polylactic acid film in the technical scheme in food packaging. The rare earth nucleating agent in the modified polylactic acid film has good compatibility with polylactic acid and is not easy to separate out, so the film can be applied to food packaging.
Detailed Description
The invention provides a rare earth nucleating agent which is a lactic acid rare earth complex. In the invention, the rare earth elements in the lactic acid rare earth complex preferably comprise one or more of cerium, lanthanum, neodymium and samarium; when the rare earth element includes several of cerium, lanthanum, neodymium and samarium, cerium and samarium are further preferable. In the invention, the rare earth element in the rare earth nucleating agent can generate strong coordination effect on carboxylic acid in polylactic acid, and a lactic acid ligand in the rare earth nucleating agent is a synthetic raw material of the polylactic acid and has good compatibility with the polylactic acid; the rare earth nucleating agent can improve the crystallinity of the polylactic acid by a dual mechanism of heterogeneous nucleation crystallization and climbing crystallization, and has an obvious crystallization promoting effect. Therefore, the rare earth nucleating agent provided by the invention has good compatibility with polylactic acid, is not easy to precipitate, can obviously improve the crystallinity of the polylactic acid, and improves the comprehensive performance of the polylactic acid.
The invention provides a preparation method of the rare earth nucleating agent in the technical scheme, which comprises the following steps:
mixing a ligand compound, a surfactant, a coupling agent and water to obtain a first solution; the ligand compound comprises lactic acid and/or sodium lactate;
dissolving a rare earth compound to obtain a second solution; the rare earth compound comprises one or more of rare earth nitrate, rare earth chloride and rare earth oxalate;
dropwise adding the second solution into the first solution to perform a coordination reaction to obtain a precipitate; and sequentially centrifuging, filtering and drying the precipitate to obtain the rare earth nucleating agent.
The invention mixes ligand compound, surface active agent, coupling agent and water to obtain the first solution. In the present invention, the ligand compound includes lactic acid and/or sodium lactate; the lactic acid and sodium lactate used in the present invention are not particularly limited, and commercially available lactic acid and sodium lactate known to those skilled in the art may be used. In the present invention, the surfactant preferably includes a biosurfactant and/or a nonionic surfactant; the present invention does not require the use of the biosurfactants, such as in particular sophorolipids, and of the nonionic surfactants, such as in particular polyoxyethylene fatty alcohol ethers or diethylene glycol butyl ethers, which are well known to the person skilled in the art. In the invention, the surfactant is used for dispersing the precipitated particles, so that the particle size of the powder is easy to control. In the invention, the coupling agent preferably comprises one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent; the silane coupling agent, such as in particular KH550, KH560 or KH570, the titanate coupling agent, such as in particular TMC-201, TMC-102, TMC-101, TMC-311, TMC-2, TMC-4 or TMC-27, and the aluminate coupling agent, such as in particular DL-411, LS-60 or HW-988, are not particularly required for the present invention, as are the corresponding coupling agents well known to the person skilled in the art. In the invention, the coupling agent is used for carrying out surface treatment on the coordination reaction product so as to improve the compatibility with polylactic acid.
In the invention, the mass concentration of the ligand compound in the first solution is preferably 55-60%; the pH value of the first solution is preferably 6-9, the sodium lactate and the lactic acid serving as ligand compounds can be fully ionized in a medium-alkaline environment with the pH value of 6-9, lactate ions are formed in the solution, the coordination reaction with rare earth ions is facilitated, the reaction time under an acidic condition is long, and the preparation of products is not facilitated. In the present invention, the molar ratio of the rare earth compound, the ligand compound, the surfactant and the coupling agent is preferably 1: (0.5-9): (0.0005-0.02): (0.0005 to 0.02), more preferably 1: (1-6): (0.001-0.01): (0.001 to 0.01), more preferably 1: (2-4): (0.002-0.005): (0.002-0.005). In the present invention, the method of mixing the ligand compound, the surfactant, the coupling agent and water is preferably: mixing the ligand compound with water to obtain a ligand compound water solution with the mass concentration of 55-60%; and adjusting the pH value of the ligand compound aqueous solution to 6-9, and then mixing the ligand compound aqueous solution with a surfactant and a coupling agent to obtain the first solution. In the present invention, the method of adjusting the pH is preferably: dropwise adding an alkaline reagent into the ligand compound aqueous solution; the alkaline agent is preferably sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or ammonia.
The invention dissolves the rare earth compound to obtain a second solution. In the invention, the rare earth compound comprises one or more of rare earth nitrate, rare earth chloride and rare earth oxalate, and is preferably cerium nitrate, cerium chloride, lanthanum chloride,
One or more of neodymium acid and samarium chloride; when the rare earth compound is cerium nitrate, cerium chloride, lanthanum chloride,
When some of neodymium acid and samarium chloride are used, the invention can treat cerium nitrate, cerium chloride, lanthanum chloride,
The mixing proportion of the neodymium acid and the samarium chloride has no special requirement and can be mixed in any proportion; when the rare earth compound is cerium nitrate, cerium chloride, lanthanum chloride,
In the case of some of neodymium acid and samarium chloride, samarium chloride and cerium chloride are more preferable. The source of the rare earth compound is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used. The present invention does not particularly require a solvent for dissolving the rare earth compound, and any solvent capable of dissolving the rare earth compound may be used, specifically, ethanol, water or isoamyl alcohol. The concentration of the second solution is not particularly required, and the rare earth compound can be sufficiently dissolved.
After a first solution and a second solution are obtained, dropwise adding the second solution into the first solution for coordination reaction to obtain a precipitate; and sequentially centrifuging, filtering and drying the precipitate to obtain the rare earth nucleating agent. In the invention, the temperature of the coordination reaction is preferably 30-60 ℃, specifically 30 ℃, 40 ℃, 50 ℃ and 60 ℃, and the temperature of the coordination reaction is preferably realized by a water bath heating mode; the time of the coordination reaction is preferably 2-24 h, more preferably 4-12 h, and the time of the coordination reaction is calculated from the completion of the dropwise addition of the second solution; the second solution is preferably dripped within 0.5-2 h. In the present invention, the coordination reaction is preferably carried out under stirring. In the coordination reaction process, the rare earth ions in the rare earth compound and the lactic acid ions in the ligand compound are subjected to coordination reaction to form complex precipitates. In the invention, the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 60-100 ℃, and the time is preferably 6-24 h. After drying, the invention also preferably ball-milling the obtained dried product to obtain the rare earth nucleating agent; the particle size of the rare earth nucleating agent is preferably 10 μm or less, more preferably 100nm to 5 μm, and still more preferably 800nm to 2 μm.
The preparation method of the rare earth nucleating agent provided by the invention is simple in process, easy to operate and convenient for large-scale production.
The invention provides the application of the rare earth nucleating agent in the technical scheme or the rare earth nucleating agent prepared by the preparation method in the technical scheme in polylactic acid materials.
The invention provides a high-crystallinity modified polylactic acid film which comprises the following preparation raw materials in parts by mass:
the rare earth nucleating agent is the rare earth nucleating agent prepared by the technical scheme or the preparation method of the technical scheme.
The high-crystallinity modified polylactic acid film comprises 57.5-99.5 parts by mass of polylactic acid, preferably 70-95 parts by mass of polylactic acid, and more preferably 78.5-84 parts by mass of polylactic acid. The polylactic acid of the present invention is not particularly limited, and commercially available polylactic acid known to those skilled in the art may be used, specifically: the polylactic acids manufactured by Dadalco Bien company are L175, L130 and LX530, the polylactic acids manufactured by NatureWorks of America are 4032D and 3001D, the polylactic acids manufactured by Anpico Feng original company are FY801, FY802 and FY601, and the polylactic acids manufactured by Zhejiang Haizhong company are REVODE 110.
Based on the mass parts of polylactic acid, the high-crystallinity modified polylactic acid film provided by the invention comprises 0.5-2.5 parts of rare earth nucleating agent, preferably 1-2 parts, and further preferably 1-1.5 parts.
The high-crystallinity modified polylactic acid film provided by the invention comprises 0-20 parts of plasticizer, preferably 0-15 parts, more preferably 5-15 parts, and further preferably 10-15 parts by mass of polylactic acid. In the present invention, the plasticizer preferably includes one or more of polyethylene glycol (PEG), tributyl citrate (TBC) and Epoxidized Soybean Oil (ESO).
The high-crystallinity modified polylactic acid film provided by the invention comprises 0-20 parts of toughening agent by mass, preferably 5-20 parts by mass. In the present invention, the toughening agent preferably includes one or more of natural rubber (ER), Polycaprolactone (PCL), and polybutylene adipate terephthalate (PBAT).
The polylactic acid film provided by the invention has higher crystallinity and excellent comprehensive performance due to the addition of the rare earth nucleating agent; in addition, the rare earth nucleating agent, the plasticizer and the toughening agent can be used for synergistically modifying the polylactic acid, so that the comprehensive performance of the polylactic acid can be further improved, and the practical application requirements can be better met.
The invention provides a preparation method of a high-crystallinity modified polylactic acid film, which comprises the following steps:
carrying out melt blending on the rare earth nucleating agent, the polylactic acid, the plasticizer and the toughening agent to obtain a blend;
sequentially carrying out hot pressing and annealing on the blend to obtain the high-crystallinity modified polylactic acid film; the annealing temperature is 90-110 ℃, and the annealing time is 1-10 min.
The rare earth nucleating agent, the polylactic acid, the plasticizer and the toughening agent are subjected to melt blending to obtain a blend. In the present invention, the melt blending is preferably carried out in a torque rheometer, which is not particularly required by the present invention and is well known to those skilled in the art, and is advantageous for achieving a good blending effect. In the invention, the temperature of the melt blending is preferably 170-200 ℃, more preferably 175-190 ℃; the rotation speed of the melt blending is preferably 45-60 rpm, and more preferably 50-55 rpm; the time for melt blending is preferably 4 to 10min, and more preferably 5 to 10 min.
After the blend is obtained, the blend is sequentially subjected to hot pressing and annealing to obtain the high-crystallinity modified polylactic acid film. In the invention, the hot pressing temperature is preferably 165-190 ℃, and more preferably 175-180 ℃; the hot pressing pressure is preferably 10-15 MPa, and more preferably 13-15 MPa; the hot pressing time is preferably 30-120 s, and more preferably 45-90 s; the hot pressing is preferably carried out in a press vulcanizer. In the present invention, the hot pressing method is preferably: cutting the blend into small blocks to obtain blocky blends; and (3) placing the blocky blend into a flat vulcanizing machine, preheating for 2-8 min at 165-190 ℃, and then applying pressure of 10-15 MPa to carry out hot pressing on the preheated blend. In the invention, the annealing temperature is 90-110 ℃, preferably 90-100 ℃, and the time is 1-10 min, preferably 2-8 min; the annealing is preferably carried out in an oven. The rare earth nucleating agent plays a role in heterogeneous nucleation in the polylactic acid, a plurality of fine crystal nuclei are quickly formed in the polylactic acid in the annealing process, the crystal nuclei grow until being contacted with each other along with the extension of the annealing time, and the molecular chain in the polylactic acid can quickly form a plurality of small crystal nuclei through climbing crystallization due to the good compatibility of the rare earth nucleating agent and the polylactic acid, so that the polylactic acid with high crystallinity is obtained. In the present invention, the thickness of the high-crystallinity modified polylactic acid film is preferably 15 to 2000. mu.m, more preferably 100 to 500. mu.m.
The preparation method of the high-crystallinity modified polylactic acid film provided by the invention is simple in process and easy to operate.
The invention provides the application of the high-crystallinity modified polylactic acid film in the technical scheme or the high-crystallinity modified polylactic acid film prepared by the preparation method in the technical scheme in food packaging. The rare earth nucleating agent in the modified polylactic acid film has good compatibility with polylactic acid and is not easy to separate out, so the film can be applied to food packaging.
The following will describe the rare earth nucleating agent and its preparation method and application, and the high-crystallinity modified polylactic acid film and its preparation method and application in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Preparation of rare earth nucleating agent
Adjusting the pH value of a lactic acid aqueous solution (mass concentration is 55%) to 7, and then adding the lactic acid aqueous solution after the pH value is adjusted, a biosurfactant sophorolipid and a silane coupling agent KH550 into a three-neck flask to obtain a first solution;
dissolving cerium nitrate in ethanol to obtain a second solution;
controlling the heating temperature of the water bath to be 30 ℃, gradually dripping the second solution into the first solution, wherein the molar ratio of the cerium nitrate to the lactic acid to the sophorolipid to the KH550 is 1: 3: 0.002: 0.002, the second solution is dripped within 0.5h, and is stirred for 2h after dripping to carry out coordination reaction, so that cerium lactate white precipitate is obtained; and centrifuging and filtering the white cerium lactate precipitate, and drying in a vacuum oven at 70 ℃ for 24 hours to obtain cerium lactate powder, namely the rare earth nucleating agent.
(2) Preparation of high-crystallinity modified polylactic acid film
Mixing polylactic acid (PLA), a rare earth nucleating agent, a plasticizer polyethylene glycol (PEG) and a toughening agent Polycaprolactone (PCL) according to a mass ratio of 79: 1: 15: 5, adding the mixture into a torque rheometer, and carrying out melt blending for 5min at the temperature of 175 ℃ and the rpm of 60 to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 2min at 175 ℃, then hot-pressing for 60s at 15MPa, and finally placing the small blocks in an oven at 90 ℃ for annealing for 8min to obtain a high-crystallinity modified polylactic acid film with the thickness of about 100 mu m, wherein the crystallinity is 49% (the crystallinity is measured by DSC, and the measurement condition is that the temperature is increased to 200 ℃ at the temperature rising rate of 10 ℃/min under the protection of nitrogen).
Example 2
(1) Preparation of rare earth nucleating agent
Adjusting the pH value of a sodium lactate aqueous solution (with the mass concentration of 60%) to 8, and then adding the sodium lactate aqueous solution with the pH value adjusted, a nonionic surfactant polyoxyethylene fatty alcohol ether and a silane coupling agent KH560 into a three-neck flask to obtain a first solution;
dissolving lanthanum chloride in isoamyl alcohol to obtain a second solution;
controlling the water bath heating temperature to be 40 ℃, gradually dripping the second solution into the first solution, wherein the molar ratio of lanthanum chloride, sodium lactate, polyoxyethylene fatty alcohol ether and KH560 is 1: 4: 0.002: 0.005, dripping the second solution within 1h, and stirring for 5h to perform coordination reaction to obtain a white lanthanum lactate precipitate; and centrifuging and filtering the lanthanum lactate white precipitate, and drying in a vacuum oven at 80 ℃ for 24h to obtain lanthanum lactate powder, namely the rare earth nucleating agent.
(2) Preparation of high-crystallinity modified polylactic acid film
Mixing polylactic acid (PLA), a rare earth nucleating agent and a plasticizer tributyl citrate (TBC) according to a mass ratio of 79.5: 0.5: 20, adding the mixture into a torque rheometer, and carrying out melt blending for 4min at the temperature of 170 ℃ and the rpm of 45 to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 6min at 165 ℃, then hot-pressing for 90s at 10MPa, and finally placing the small blocks in a 100 ℃ oven for annealing for 5min to obtain the high-crystallinity modified polylactic acid film with the crystallinity of 42%.
Example 3
(1) Preparation of rare earth nucleating agent
Adjusting the pH value of a sodium lactate aqueous solution (with the mass concentration of 60%) to 6, and then adding the sodium lactate aqueous solution after the pH value is adjusted, a nonionic surfactant diethylene glycol monobutyl ether and a silane coupling agent KH570 into a three-neck flask to obtain a first solution;
will be provided with
Dissolving neodymium acid in water to obtain a second solution;
controlling the heating temperature of the water bath to be 60 ℃, gradually dripping the second solution into the first solution,
neodymium acidThe molar ratio of sodium lactate, diethylene glycol monobutyl ether and KH570 is 1: 6: 0.004: 0.004, dripping the second solution within 2 hours, and stirring for 24 hours to perform coordination reaction to obtain a neodymium lactate white precipitate; and centrifuging and filtering the neodymium lactate white precipitate, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain neodymium lactate powder, namely the rare earth nucleating agent.
(2) Preparation of high-crystallinity modified polylactic acid film
Polylactic acid (PLA), a rare earth nucleating agent and a toughening agent Polycaprolactone (PCL) are mixed according to a mass ratio of 78.5: 1.5: 20, adding the mixture into a torque rheometer, and carrying out melt blending for 5min at 180 ℃ and 50rpm to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 4min at 180 ℃, then hot-pressing for 30s at 15MPa, and finally placing the small blocks in a drying oven at 110 ℃ for annealing for 1min to obtain the high-crystallinity modified polylactic acid film, wherein the crystallinity is 46%.
Example 4
(1) Preparation of rare earth nucleating agent
Adjusting the pH value of a lactic acid aqueous solution (with the mass concentration of 60%) to 9, and then adding the lactic acid aqueous solution after the pH value is adjusted, a biosurfactant sophorolipid and a silane coupling agent KH560 into a three-neck flask to obtain a first solution;
dissolving samarium chloride and cerium chloride in ethanol to obtain a second solution;
controlling the heating temperature of the water bath to be 30 ℃, gradually dripping the second solution into the first solution, and mixing the first solution and the second solution according to the molar ratio of samarium chloride, cerium chloride, lactic acid, sophorolipid and KH560 of 0.7: 0.3: 5: 0.003: 0.003, dripping the second solution within 0.5h, and stirring for 4h to perform coordination reaction to obtain white precipitate of samarium cerium lactate; and centrifuging and filtering the white precipitate of the samarium cerium lactate, and drying the white precipitate in a vacuum oven at 100 ℃ for 6 hours to obtain samarium cerium lactate powder, namely the rare earth nucleating agent.
(2) Preparation of high-crystallinity modified polylactic acid film
Mixing polylactic acid (PLA), a rare earth nucleating agent, a plasticizer tributyl citrate (TBC) and a toughening agent natural rubber (ER) according to a mass ratio of 83: 2: 5:10, adding the mixture into a torque rheometer, and carrying out melt blending for 10min at 200 ℃ and 45rpm to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 8min at 180 ℃, then hot-pressing for 120s at 13MPa, and finally placing the small blocks in a 90 ℃ oven for annealing for 10min to obtain the high-crystallinity modified polylactic acid film, wherein the crystallinity is 44%.
Example 5
(1) Preparation of rare earth nucleating agent
Adjusting the pH value of a sodium lactate aqueous solution (mass concentration is 55%) to 7, and then adding the sodium lactate aqueous solution after the pH value is adjusted, a nonionic surfactant diethylene glycol monobutyl ether and a silane coupling agent KH550 into a three-neck flask to obtain a first solution;
dissolving cerium chloride in isoamyl alcohol to obtain a second solution;
controlling the heating temperature of the water bath to be 50 ℃, gradually dripping the second solution into the first solution, wherein the molar ratio of cerium chloride, sodium lactate, diethylene glycol butyl ether and KH550 is 1: 5: 0.003: 0.003, the second solution is dripped within 0.5h, and is stirred for 12h after dripping for coordination reaction to obtain cerium lactate white precipitate; and centrifuging and filtering the white cerium lactate precipitate, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain cerium lactate powder, namely the rare earth nucleating agent.
(2) Preparation of high-crystallinity modified polylactic acid film
Polylactic acid (PLA), a rare earth nucleating agent, a plasticizer Epoxidized Soybean Oil (ESO) and a toughening agent polybutylene adipate terephthalate (PBAT) are mixed according to a mass ratio of 84: 1: 15: 5, adding the mixture into a torque rheometer, and carrying out melt blending for 5min at 180 ℃ and 60rpm to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 6min at 180 ℃, then hot-pressing for 45s at 15MPa, and finally placing the small blocks in a 90 ℃ oven for annealing for 5min to obtain the high-crystallinity modified polylactic acid film, wherein the crystallinity is 46%.
Example 6
(1) Preparation of rare earth nucleating agent
Adjusting the pH value of a sodium lactate aqueous solution (mass concentration is 55%) to 8, and then adding the sodium lactate aqueous solution after the pH value is adjusted, a nonionic surfactant polyoxyethylene fatty alcohol ether and a silane coupling agent KH570 into a three-neck flask to obtain a first solution;
dissolving cerium nitrate in ethanol to obtain a second solution;
controlling the heating temperature of the water bath to be 30 ℃, gradually dripping the second solution into the first solution, wherein the molar ratio of the cerium nitrate to the sodium lactate to the polyoxyethylene fatty alcohol ether to the KH570 is 1: 3: 0.004: 0.002, the second solution is dripped within 0.5h, and is stirred for 4h after dripping to carry out coordination reaction, so that cerium lactate white precipitate is obtained; and centrifuging and filtering the white cerium lactate precipitate, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain cerium lactate powder, namely the rare earth nucleating agent.
(2) Preparation of high-crystallinity modified polylactic acid film
Polylactic acid (PLA) and a rare earth nucleating agent are mixed according to a mass ratio of 98.5: 1.5, adding the mixture into a torque rheometer, and carrying out melt blending for 5min at 190 ℃ and 55rpm to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 6min at 180 ℃, then hot-pressing for 60s at 10MPa, and finally placing the small blocks in a 100 ℃ oven for annealing for 2min to obtain the high-crystallinity modified polylactic acid film, wherein the crystallinity is 37%.
Example 7
(1) Preparation of rare earth nucleating agent
Adjusting the pH value of a sodium lactate aqueous solution (mass concentration is 55%) to 8, and then adding the sodium lactate aqueous solution after pH value adjustment, a biosurfactant sophorolipid and a silane coupling agent KH570 into a three-neck flask to obtain a first solution;
dissolving cerium nitrate in ethanol to obtain a second solution;
controlling the heating temperature of the water bath to be 30 ℃, gradually dripping the second solution into the first solution, wherein the molar ratio of the cerium nitrate to the sodium lactate to the sophorolipid to the KH570 is 1: 3: 0.004: 0.002, the second solution is dripped within 0.5h, and is stirred for 4h after dripping to carry out coordination reaction, so that cerium lactate white precipitate is obtained; and centrifuging and filtering the white cerium lactate precipitate, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain cerium lactate powder, namely the rare earth nucleating agent.
(2) Preparation of high-crystallinity modified polylactic acid film
Polylactic acid (PLA), a rare earth nucleating agent, a plasticizer tributyl citrate (TBC) and a toughening agent Polycaprolactone (PCL) are mixed according to a mass ratio of 83.5: 1.5: 10: 5, adding the mixture into a torque rheometer, and carrying out melt blending for 5min at 190 ℃ and 55rpm to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 6min at 180 ℃, then hot-pressing for 60s at 10MPa, and finally placing the small blocks in a 100 ℃ oven for annealing for 2min to obtain the high-crystallinity modified polylactic acid film, wherein the crystallinity is 52%.
COMPARATIVE EXAMPLE 1 (COMPARATIVE EXAMPLE 7)
Preparing a modified polylactic acid film:
mixing polylactic acid (PLA) and plasticizer tributyl citrate (TBC) according to a mass ratio of 90: 10, adding the mixture into a torque rheometer, and carrying out melt blending for 5min at 190 ℃ and 55rpm to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 6min at 180 ℃, then hot-pressing for 60s at 10MPa, and finally placing the small blocks in a 100 ℃ oven for annealing for 2min to obtain the modified polylactic acid film with the crystallinity of 22%.
COMPARATIVE EXAMPLE 2 (COMPARATIVE EXAMPLE 7)
Preparing a modified polylactic acid film:
polylactic acid (PLA) and a toughening agent Polycaprolactone (PCL) are mixed according to a mass ratio of 95: 5, adding the mixture into a torque rheometer, and carrying out melt blending for 5min at 190 ℃ and 55rpm to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 6min at 180 ℃, then hot-pressing for 60s at 10MPa, and finally placing the small blocks in a 100 ℃ oven for annealing for 2min to obtain the modified polylactic acid film with the crystallinity of 19%.
COMPARATIVE EXAMPLE 3 (COMPARATIVE EXAMPLE 7)
Preparing a modified polylactic acid film:
mixing polylactic acid (PLA), a plasticizer tributyl citrate (TBC) and a toughening agent Polycaprolactone (PCL) according to a mass ratio of 85: 10: 5, adding the mixture into a torque rheometer, and carrying out melt blending for 5min at 190 ℃ and 55rpm to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 6min at 180 ℃, then hot-pressing for 60s at 10MPa, and finally placing the small blocks in a 100 ℃ oven for annealing for 2min to obtain the modified polylactic acid film with the crystallinity of 24%.
COMPARATIVE EXAMPLE 4 (COMPARATIVE EXAMPLE 7)
Preparing a modified polylactic acid film:
adding polylactic acid (PLA) into a torque rheometer, and carrying out melt blending for 5min at 190 ℃ and 55rpm to obtain a blend;
cutting the blend into small blocks, placing the small blocks in a flat vulcanizing machine, preheating for 6min at 180 ℃, then hot-pressing for 60s at 10MPa, and finally placing the small blocks in a 100 ℃ oven for annealing for 2min to obtain the polylactic acid film with the crystallinity of 17%.
The crystallinity and the overall properties of the modified polylactic acid films prepared in examples 1 to 7 and comparative examples 1 to 4 are summarized in table 1:
TABLE 1 crystallinity and combination properties of modified polylactic acid films obtained in examples 1 to 7 and comparative examples 1 to 4
The embodiment shows that the high-crystallinity modified polylactic acid film provided by the invention has higher crystallinity and excellent comprehensive performance due to the addition of the rare earth nucleating agent; in addition, the rare earth nucleating agent, the plasticizer and the toughening agent can be used for synergistically modifying the polylactic acid, so that the comprehensive performance of the polylactic acid is further improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The rare earth nucleating agent is characterized by being a lactic acid rare earth complex.
2. The rare earth nucleating agent as defined in claim 1, wherein the rare earth element in the lactic acid rare earth complex comprises one or more of cerium, lanthanum, neodymium and samarium.
3. A process for producing a rare earth nucleating agent according to claim 1 or 2, characterized by comprising the steps of:
mixing a ligand compound, a surfactant, a coupling agent and water to obtain a first solution; the ligand compound comprises lactic acid and/or sodium lactate;
dissolving a rare earth compound to obtain a second solution; the rare earth compound comprises one or more of rare earth nitrate, rare earth chloride and rare earth oxalate;
dropwise adding the second solution into the first solution to perform a coordination reaction to obtain a precipitate; and sequentially centrifuging, filtering and drying the precipitate to obtain the rare earth nucleating agent.
4. The preparation method according to claim 3, wherein the mass concentration of the ligand compound in the first solution is 55-60%; the pH value of the first solution is 6-9;
the molar ratio of the rare earth compound, the ligand compound, the surfactant and the coupling agent is 1 (0.5-9): 0.0005-0.02);
the temperature of the coordination reaction is 30-60 ℃, and the time is 2-24 h.
5. The rare earth nucleating agent of any one of claims 1 to 2 or the rare earth nucleating agent prepared by the preparation method of any one of claims 3 to 4 is applied to polylactic acid materials.
6. The high-crystallinity modified polylactic acid film is characterized by comprising the following preparation raw materials in parts by mass:
the rare earth nucleating agent is the rare earth nucleating agent of claim 1 or 2 or the rare earth nucleating agent prepared by the preparation method of any one of claims 3 to 4.
7. The high-crystallinity modified polylactic acid film according to claim 6, wherein the plasticizer comprises one or more of polyethylene glycol, tributyl citrate and epoxidized soybean oil; the toughening agent comprises one or more of natural rubber, polycaprolactone and polybutylene adipate/terephthalate.
8. The method for preparing a high-crystallinity modified polylactic acid film according to claim 6 or 7, comprising the steps of:
carrying out melt blending on the rare earth nucleating agent, the polylactic acid, the plasticizer and the toughening agent to obtain a blend;
sequentially carrying out hot pressing and annealing on the blend to obtain the high-crystallinity modified polylactic acid film; the annealing temperature is 90-110 ℃, and the annealing time is 1-10 min.
9. The method of manufacturing according to claim 8, wherein the melt blending is performed in a torque rheometer; the temperature of the melt blending is 170-200 ℃, the rotating speed is 45-60 rpm, and the time is 4-10 min;
the hot pressing temperature is 165-190 ℃, the pressure is 10-15 MPa, and the time is 30-120 s.
10. Use of the high-crystallinity modified polylactic acid film according to any one of claims 6 to 7 or the high-crystallinity modified polylactic acid film prepared by the preparation method according to any one of claims 8 to 9 in food packaging.
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| CN115491003A (en) * | 2022-09-14 | 2022-12-20 | 包头稀土研究院 | Application of rare earth amino acid complex, polylactic acid composition and preparation method thereof |
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| US20030010722A1 (en) * | 2001-07-16 | 2003-01-16 | Dudley John Mills | Removal of phosphate from water |
| CN103880872A (en) * | 2014-03-28 | 2014-06-25 | 中国科学院长春应用化学研究所 | Preparation method and application of lactic acid rare earth complex and rare earth catalyst |
| CN111849205A (en) * | 2020-08-03 | 2020-10-30 | 包头稀土研究院 | Compound, polylactic acid composite material, preparation method and application |
| CN112898752A (en) * | 2021-02-03 | 2021-06-04 | 湖南工业大学 | High-crystallinity polylactic acid material and preparation method thereof |
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| US20030010722A1 (en) * | 2001-07-16 | 2003-01-16 | Dudley John Mills | Removal of phosphate from water |
| CN103880872A (en) * | 2014-03-28 | 2014-06-25 | 中国科学院长春应用化学研究所 | Preparation method and application of lactic acid rare earth complex and rare earth catalyst |
| CN111849205A (en) * | 2020-08-03 | 2020-10-30 | 包头稀土研究院 | Compound, polylactic acid composite material, preparation method and application |
| CN112898752A (en) * | 2021-02-03 | 2021-06-04 | 湖南工业大学 | High-crystallinity polylactic acid material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115491003A (en) * | 2022-09-14 | 2022-12-20 | 包头稀土研究院 | Application of rare earth amino acid complex, polylactic acid composition and preparation method thereof |
| CN115491003B (en) * | 2022-09-14 | 2023-08-15 | 包头稀土研究院 | Application of rare earth amino acid complex, polylactic acid composition and preparation method thereof |
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