CN115612072A - Method for preparing high-transparency high-toughness polylactic acid-based material - Google Patents
Method for preparing high-transparency high-toughness polylactic acid-based material Download PDFInfo
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- CN115612072A CN115612072A CN202211402178.XA CN202211402178A CN115612072A CN 115612072 A CN115612072 A CN 115612072A CN 202211402178 A CN202211402178 A CN 202211402178A CN 115612072 A CN115612072 A CN 115612072A
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- lactide
- polylactic acid
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- toughness
- transparency
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- 239000000463 material Substances 0.000 title claims abstract description 81
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 66
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 17
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 44
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000007599 discharging Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 238000011049 filling Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002667 nucleating agent Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 229920000954 Polyglycolide Polymers 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000004633 polyglycolic acid Substances 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000000655 anti-hydrolysis Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- JJTUDXZGHPGLLC-QWWZWVQMSA-N (3r,6r)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@@H](C)OC1=O JJTUDXZGHPGLLC-QWWZWVQMSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 101100083853 Homo sapiens POU2F3 gene Proteins 0.000 description 1
- 101100058850 Oryza sativa subsp. japonica CYP78A11 gene Proteins 0.000 description 1
- 101100352374 Oryza sativa subsp. japonica PLA3 gene Proteins 0.000 description 1
- RPIJSAGCGJCBGU-UHFFFAOYSA-L P([O-])([O-])=O.C1(=CC=CC=C1)[Zn+2] Chemical compound P([O-])([O-])=O.C1(=CC=CC=C1)[Zn+2] RPIJSAGCGJCBGU-UHFFFAOYSA-L 0.000 description 1
- 101150059175 PLA1 gene Proteins 0.000 description 1
- 102100026466 POU domain, class 2, transcription factor 3 Human genes 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 102100026918 Phospholipase A2 Human genes 0.000 description 1
- 101710096328 Phospholipase A2 Proteins 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polybutylene adipate terephthalate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- VYXPIEPOZNGSJX-UHFFFAOYSA-L zinc;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Zn+2].[O-]P([O-])(=O)C1=CC=CC=C1 VYXPIEPOZNGSJX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the field of polylactic acid copolymerization modification, and aims to provide a method for preparing a high-transparency and high-toughness polylactic acid-based material. The method comprises the following steps: adding three monomers of L-lactide, glycolide and D-lactide and a catalyst into a polymerization kettle, and mechanically stirring and uniformly mixing; heating to 30-60 ℃ under the condition of 50-500 Pa and keeping mechanical stirring, and keeping for 0.5-2 h; then inert gas is filled as protective gas, the temperature is raised to 120-220 ℃, and the reaction lasts for 0.5-8 h; and after the reaction is finished, discharging from the bottom of the kettle, and granulating to obtain the polylactic acid-based material with high transparency and high toughness. Compared with the prior art, the invention has the beneficial effects that: the polymerization process is simple, the technical cost is low, and large-scale industrial production can be realized; the usage amount of the D-lactide is low, so that the raw material cost of the polylactic acid-based material cannot be greatly increased; the toughness of the polylactic acid-based material can be regulated and controlled by changing the using amount of glycolide.
Description
Technical Field
The invention relates to the field of polylactic acid copolymerization modification, in particular to a preparation method of a high-toughness and high-transparency polylactic acid-based material.
Background
The disposable non-degradable plastic products have large usage amount and low recycling rate, cause serious pollution to soil and marine environment, bring damage which is difficult to eliminate to ecological environment, seriously harm human health at the same time, and control of plastic pollution becomes a common consensus of the international society.
The polylactic acid material has better mechanical property, lower price and cost compared with other degradation materials, and smaller replacement resistance. Among them, the degradable material is mainly applied to the fields of tableware, straws and the like, and is just the replacement of traditional plastics by polylactic acid. However, polylactic acid materials are brittle and have low transparency, which greatly limits the application of polylactic acid materials in the high-end packaging field and the 3D printing field. Modification of polylactic acid materials is a feasible research direction, but the traditional modification method can only improve the toughness or transparency of the polylactic acid materials, and the polylactic acid materials with high toughness and high transparency are difficult to obtain. For example, the toughness of polylactic acid materials is generally improved by adding a plasticizer (such as tributyl acetylcitrate, etc.) or blending with a high-toughness elastomer (such as polyurethane, etc.), but the transparency of the polylactic acid materials is often low or even completely opaque. The transparency of the polylactic acid material is improved by adding a special nucleating agent, so that the crystal grains of the crystallized polylactic acid material are reduced, but the toughness of the material is generally unchanged or even weakened. Therefore, the preparation of the polylactic acid material with high transparency and high toughness is difficult, and related documents are rarely reported.
Therefore, a new process capable of simultaneously realizing high transparency and high toughness of the polylactic acid material is provided, and the method has practical significance for promoting plastic pollution treatment.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method of a high-transparency and high-toughness polylactic acid-based material.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the high-transparency high-toughness polylactic acid-based material comprises the following steps:
(1) Adding three monomers of L-lactide, glycolide and D-lactide and a catalyst into a polymerization kettle, and mechanically stirring and uniformly mixing; controlling the adding amount of the raw material components to ensure that the mass ratio of the L-lactide, the glycolide, the D-lactide and the catalyst is 100: 1-30: 1-5: 0.01-1;
the chemical structural formulas of L-lactide (left), glycolide (middle) and D-lactide (right) are shown as follows:
(2) Under the condition of 50-500 Pa and keeping mechanical stirring, the temperature of the polymerization kettle is raised to 30-60 ℃ and is maintained for 0.5-2 h; then, filling inert gas serving as protective gas into the polymerization kettle, raising the temperature to 120-220 ℃, and reacting for 0.5-8 h;
(3) And after the reaction is finished, discharging from the bottom of the kettle, and granulating to obtain the polylactic acid-based material with high transparency and high toughness.
In a preferred embodiment of the present invention, the catalyst is any one of a tin-based catalyst, a titanium-based catalyst, and a zinc-based catalyst.
In a preferred embodiment of the present invention, the catalyst is any one of stannous octoate, tetraisopropyl titanate, and zinc oxide.
As a preferred embodiment of the present invention, the inert gas is nitrogen or argon.
As a preferable scheme of the present invention, the step (1) further comprises adding an auxiliary agent, wherein the auxiliary agent is any one or more of an initiator, an antioxidant, an anti-hydrolysis agent or a nucleating agent.
Description of the inventive principles:
in the conventional process technology, polylactic acid is prepared by ring-opening polymerization of single L-lactide, and is brittle and easy to crystallize, so that the transparency is reduced. In the invention, a small amount of glycolide, D-lactide and L-lactide are subjected to ring-opening polymerization together to obtain the polylactic acid-based material with high toughness and high transparency. The invention principle is as follows: (1) Due to the addition of a small amount of glycolide, on one hand, a polyglycolic acid unit can be formed in the polylactic acid-based material, and the glass transition temperature of the polyglycolic acid unit is far lower than that of the polylactic acid unit, so that the flexibility of a molecular chain is improved, and the toughening of the polylactic acid-based material is realized; on the other hand, a small amount of polyglycolic acid unit does not participate in the crystallization of polylactic acid, and similarly to the chemical defect, the crystallization of polylactic acid can be suppressed and the melting point of the material can be lowered. (2) Due to the addition of the D-lactide, the optical regularity of the poly-L-lactic acid can be further disturbed, and the crystallization of the poly-L-lactic acid is greatly inhibited, so that the product has high transparency, and finally the polylactic acid-based material has high toughness and high transparency.
The traditional polylactic acid-based materials are generally modified by adding a plasticizer or blending with high-toughness materials, such as polyurethane, polybutylene adipate terephthalate (PBAT), and the like, but the modified materials have poor transparency, and the high-toughness and high-transparency polylactic acid-based materials are difficult to obtain.
Glycolide and D-lactide are commonly used to prepare high molecular weight polyglycolide and high gloss pure poly D-lactic acid. The published literature reports that glycolide and a small amount of L-lactide are copolymerized to prepare a modified polyglycolic acid-based material, and the material has improved toughness compared with pure polyglycolic acid, but is opaque. In addition, the mechanical property and the degradation property of the material are often emphasized in the current polylactic acid modification, and the reduction of the optical purity of the polylactic acid, such as the copolymerization of L-lactide and a small amount of D-lactide, can cause the reduction of the mechanical property, the brittleness and the too high degradation speed of the material, and cannot be generally considered for the modification of the polylactic acid material. Therefore, no relevant literature reports that glycolide and D-lactide are used as main raw materials or auxiliary materials for preparing the high-transparency high-toughness polylactic acid-based material.
The innovation of the invention is that the inertial thinking that a modifying material needs to be added in the modification of technical personnel in the field is broken through, a certain amount of glycolide and a small amount of D-lactide are added in the ring-opening polymerization process of L-lactide creatively, the optical regularity of a polylactic acid chain is damaged, the crystallization of polylactic acid is inhibited, the transparency of the material is improved, the flexibility of the polylactic acid chain is increased, the toughness of the polylactic acid material is improved, and the high-toughness and high-transparency polylactic acid-based material is finally prepared.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention only needs to simultaneously carry out ring-opening polymerization on a certain amount of glycolide, a small amount of D-lactide and L-lactide which is used as a main raw material to prepare the polylactic acid-based material, has simple polymerization process and low technical cost, and can realize large-scale industrial production.
2. The D-lactide is low in usage amount, and the raw material cost of the polylactic acid-based material cannot be greatly increased.
3. The invention can change the usage amount of glycolide and regulate the toughness of the polylactic acid-based material.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, but the scope of the invention as claimed is not limited to the scope expressed by the examples.
The raw materials used in the present invention are illustrated below: l-lactide was purchased from the company Purac; d-lactide was purchased from chemical Limited, wucang wild; glycolide was purchased from the bio-engineering company, jinan Dai, tiger. Stannous octoate, tetraisopropyl titanate, zinc oxide, stannous chloride, and tributyl acetyl citrate all available from Sigma-Aldrich; BASF Irganox 1076 is available from BASF (BASF); polycarbodiimide UN-150 was purchased from chemical Co., ltd, wande Hubei; zinc phenylphosphonate was purchased from Shanxi chemical research institute, inc. The material and type of the polymerizer are not particularly limited, and may be purchased and used directly by a known method. The method for granulating the polylactic acid-based material is not particularly limited, and may be carried out by a known method such as underwater granulation.
In the invention, other auxiliary agents such as an initiator, an antioxidant, an anti-hydrolysis agent, a nucleating agent and the like can be added in the polymerization process, and the type, the using method and the using amount of the auxiliary agents can refer to the process for preparing the polylactic acid-based material by the ring-opening polymerization of the L-lactide in the prior art. The kind of the catalyst is not limited to the one exemplified in the present invention, and can be purchased and used by referring to a known technique. The inert gas is not limited to the one exemplified in the present invention, and may be nitrogen gas, argon gas, or other known inert gases.
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
Firstly, adding L-lactide, glycolide (accounting for 1 percent of the L-lactide), D-lactide (accounting for 1 percent of the L-lactide) and stannous octoate (accounting for 0.1 percent of the L-lactide) into a polymerization kettle, and mechanically stirring and mixing; under the condition of 50Pa and mechanical stirring, the temperature of the polymerization kettle is increased to 50 ℃ and is kept for 2 hours; and secondly, filling nitrogen into the polymerization kettle, keeping mechanical stirring, raising the temperature to 150 ℃, reacting for 4 hours, discharging materials from the bottom of the kettle, and granulating to obtain the polylactic acid-based material PLA1 sample.
Example 2
Firstly, adding L-lactide, glycolide (accounting for 5 percent of the L-lactide), D-lactide (accounting for 2 percent of the L-lactide) and stannous octoate (accounting for 0.1 percent of the L-lactide) into a polymerization kettle, and mechanically stirring and mixing; under the condition of 50Pa and mechanical stirring, the temperature of the polymerization kettle is raised to 50 ℃ and kept for 2h; and secondly, filling nitrogen into the polymerization kettle, keeping mechanical stirring, raising the temperature to 150 ℃, reacting for 4 hours, discharging materials from the bottom of the kettle, and granulating to obtain the polylactic acid-based material PLA2 sample.
Example 3
Firstly, adding L-lactide, glycolide (15 percent of the L-lactide), D-lactide (3 percent of the L-lactide) and stannous octoate (0.1 percent of the L-lactide) into a polymerization kettle, and mechanically stirring and mixing; under the condition of 50Pa and mechanical stirring, the temperature of the polymerization kettle is raised to 50 ℃ and kept for 2h; and secondly, filling nitrogen into the polymerization kettle, keeping mechanical stirring, raising the temperature to 150 ℃, reacting for 4 hours, discharging materials from the bottom of the kettle, and granulating to obtain a polylactic acid-based material PLA3 sample.
Example 4
Firstly, adding L-lactide, glycolide (accounting for 30 percent of the L-lactide), D-lactide (accounting for 5 percent of the L-lactide) and stannous octoate (accounting for 0.1 percent of the L-lactide) into a polymerization kettle, and mechanically stirring and mixing; under the condition of 50Pa and mechanical stirring, the temperature of the polymerization kettle is increased to 50 ℃ and is kept for 2 hours; and secondly, filling nitrogen into the polymerization kettle, keeping mechanical stirring, raising the temperature to 150 ℃, reacting for 4 hours, discharging materials from the bottom of the kettle, and granulating to obtain a polylactic acid-based material PLA4 sample.
Example 5
Firstly, adding L-lactide, glycolide (15 percent of L-lactide), D-lactide (3 percent of L-lactide) and tetraisopropyl titanate (0.01 percent of L-lactide) into a polymerization kettle for mechanical stirring and mixing; under the condition of 200Pa and mechanical stirring, the temperature of the polymerization kettle is raised to 30 ℃ and kept for 0.5h; secondly, filling argon into the polymerization kettle, keeping mechanical stirring, raising the temperature to 120 ℃, reacting for 8 hours, discharging materials from the bottom of the kettle, and granulating to obtain the polylactic acid-based material PLA5 sample.
Example 6
Firstly, adding L-lactide, glycolide (15 percent of L-lactide), D-lactide (3 percent of L-lactide) and zinc oxide (1 percent of L-lactide) into a polymerization kettle, and mechanically stirring and mixing; under the condition of 500Pa and mechanical stirring, the temperature of the polymerization kettle is raised to 60 ℃, and the polymerization kettle is kept for 1h; secondly, filling argon into the polymerization kettle, keeping mechanical stirring, raising the temperature to 220 ℃, reacting for 0.5h, discharging materials from the bottom of the kettle, and granulating to obtain a polylactic acid-based material PLA6 sample.
Example 7
Firstly, adding L-lactide, glycolide (accounting for 30 percent of the L-lactide), D-lactide (accounting for 5 percent of the L-lactide), stannous chloride (accounting for 0.1 percent of the L-lactide), antioxidant basf Irganox 1076 (accounting for 0.3 percent of the L-lactide), plasticizer acetyl tributyl citrate (accounting for 2 percent of the L-lactide), hydrolysis resistant agent polycarbodiimide UN-150 (accounting for 2 percent of the L-lactide) and phenyl zinc phosphonate (accounting for 0.1 percent of the L-lactide) into a polymerization kettle for mechanical stirring and mixing; under the condition of 50Pa and mechanical stirring, the temperature of the polymerization kettle is raised to 50 ℃ and kept for 2h; and secondly, filling nitrogen into the polymerization kettle, keeping mechanical stirring, raising the temperature to 150 ℃, reacting for 4 hours, discharging materials from the bottom of the kettle, and granulating to obtain a polylactic acid-based material PLA7 sample.
Comparative example 1
Firstly, adding L-lactide and stannous octoate (accounting for 0.1 percent of the L-lactide) into a polymerization kettle, and mechanically stirring and mixing; under 50Pa, the temperature of the polymerization kettle is raised to 50 ℃ and kept for 2h; and secondly, filling nitrogen into the polymerization kettle, keeping mechanical stirring, raising the temperature to 150 ℃, reacting for 4 hours, discharging materials from the bottom of the kettle, and granulating to obtain a polylactic acid-based material PLA01 sample.
Comparative example 2
Firstly, adding L-lactide, glycolide (accounting for 5 percent of the L-lactide) and stannous octoate (accounting for 0.1 percent of the L-lactide) into a polymerization kettle, and mechanically stirring and mixing; under 50Pa, the temperature of the polymerization kettle is raised to 50 ℃ and kept for 2h; and secondly, filling nitrogen into the polymerization kettle, keeping mechanical stirring, raising the temperature to 150 ℃, reacting for 4 hours, discharging materials from the bottom of the kettle, and granulating to obtain the polylactic acid-based material PLA02 sample.
Comparative example 3
Firstly, adding L-lactide, D-lactide (accounting for 2 percent of the L-lactide) and stannous octoate (accounting for 0.1 percent of the L-lactide) into a polymerization kettle, and mechanically stirring and mixing; raising the temperature of the polymerization kettle to 50 ℃ under 50Pa, and keeping for 2h; and secondly, filling nitrogen into the polymerization kettle, keeping mechanical stirring, raising the temperature to 150 ℃, reacting for 4 hours, discharging the material from the bottom of the kettle, and granulating to obtain the PLA03 sample of the polylactic acid-based material.
Comparative example 4
Firstly, glycolide, L-lactide (accounting for 5 percent of the glycolide) and stannous octoate (accounting for 0.1 percent of the glycolide) are added into a polymerization kettle and mechanically stirred and mixed; under 50Pa, the temperature of the polymerization kettle is raised to 50 ℃ and kept for 2h; and secondly, filling nitrogen into a polymerization kettle, keeping mechanical stirring, raising the temperature to 150 ℃, reacting for 4 hours, discharging materials from the bottom of the kettle, and granulating to obtain the polyglycolic acid-based material PGA01 sample.
Melting point test:
the sample was heated from-20 ℃ to 250 ℃ at a heating rate of 10 ℃/min under nitrogen using a DSC25 differential scanning calorimeter (TA, USA).
And (3) testing tensile property:
and melting the sample at 200 ℃ for 2min by using a hot press, then carrying out hot pressing to form a film with the thickness of about 0.4mm, naturally cooling to room temperature, and taking out for later use. The dumbbell-shaped sample bars with the length of 50mm, the cross section width of 3mm, the thickness of 0.4mm and the gauge length of 20mm are manufactured by using a test cutter, the dumbbell-shaped sample bars are placed for 48h in a room-temperature environment after being cut to eliminate internal stress, a UTM2503 electronic universal testing machine (Shenzhen Mash & ltries & gt longitudinal and transverse company) is used for carrying out uniaxial tensile test on the sample bars at 25 ℃ at 5mm/min, at least 5 sample bars are parallelly measured on each group of samples, and the results are averaged.
And (3) impact performance test:
melting a sample at 190 ℃ by using a micro injection molding machine, then carrying out injection molding to prepare a test sample strip with the length of 80mm, the cross section width of 10mm and the thickness of 4mm, and cutting a notch with the bottom radius of 0.25mm in the middle of the sample strip by using a milling cutter after the sample strip is taken out. And during injection molding, the mold temperature is 50 ℃, the injection molding pressure is 90MPa, the time is 15s, the pressure is maintained for 15MPa, and the time is 10s. And (4) carrying out an impact strength test on the sample strips by using an cantilever beam type impact strength testing machine, testing 5 sample strips in parallel on each sample, and averaging the final results.
And (3) testing light transmittance:
a0.2 mm film sample was first crystallized isothermally in an oven at 80 ℃ for 24h, and the light transmittance of the sample at a wavelength of 550nm was measured at room temperature using a haze meter (color spectrum TH 110).
TABLE 1 melting point, elongation at break, notched impact strength and light transmittance of polylactic acid-based materials prepared in comparative examples 1 to 3 and examples 1 to 6
Table 1 shows statistics of melting point, elongation at break, notched impact strength and light transmittance of the polylactic acid-based materials prepared in comparative examples 1 to 3 and examples 1 to 7. Comparing comparative example 1 and examples 1 to 7, it is known that the addition of glycolide and D-lactide significantly improves the fracture productivity, notched impact strength and light transmittance of the polylactic acid-based material. It is understood from comparative examples 1 to 4 that the fracture productivity, the notched impact strength and the light transmittance of the polylactic acid-based material gradually increase as the addition amounts of glycolide and D-lactide increase. Taking example 4 as an example, the fracture productivity, the notched impact strength and the light transmittance were 25.7% and 25.6kJ/m, respectively 2 And 94.3%, exhibit excellent high toughness, high transparency characteristics, improved by 6 times, 16 times and 15 times in order compared to comparative example 1. From implementation to implementationExamples 3 to 6 show that when the amounts of glycolide and D-lactide were more than 15% and 3%, the melting point of the polylactic acid-based material disappeared and crystallization was not possible; therefore, the material has excellent transparency, and the light transmittance is as high as more than 87%. It is understood from example 7 that the addition of the auxiliary agent can greatly improve the data of fracture productivity, notched impact strength and light transmittance at the same time. Comparing comparative examples 1 to 4 and example 2, it is known that addition of glycolide or D-lactide alone can improve toughness or transparency to some extent, but it is difficult to improve both toughness and transparency.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (4)
1. A method for preparing a high-transparency high-toughness polylactic acid-based material is characterized by comprising the following steps:
(1) Adding three monomers of L-lactide, glycolide and D-lactide and a catalyst into a polymerization kettle, and mechanically stirring and uniformly mixing; controlling the adding amount of the raw material components to ensure that the mass ratio of the L-lactide, the glycolide, the D-lactide and the catalyst is 100: 1-30: 1-5: 0.01-1;
(2) Under the condition of 50-500 Pa and keeping mechanical stirring, the temperature of the polymerization kettle is raised to 30-60 ℃ and is maintained for 0.5-2 h; then, filling inert gas serving as protective gas into the polymerization kettle, raising the temperature to 120-220 ℃, and reacting for 0.5-8 h;
(3) And after the reaction is finished, discharging from the bottom of the kettle, and granulating to obtain the polylactic acid-based material with high transparency and high toughness.
2. The method according to claim 1, wherein the catalyst is any one of a tin-based catalyst, a titanium-based catalyst, or a zinc-based catalyst.
3. The method of claim 1, wherein the inert gas is nitrogen or argon.
4. The method of claim 1, wherein step (1) further comprises adding an auxiliary agent, wherein the auxiliary agent is any one or more of an initiator, an antioxidant, a hydrolysis-resistant agent or a nucleating agent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050203A (en) * | 1988-08-08 | 1991-03-27 | 巴特尔纪念研究院 | Come from the degradable thermoplastic plastics of rac-Lactide |
| US20030114637A1 (en) * | 2001-09-05 | 2003-06-19 | Sylwester Gogolewski | Poly(L-lactide-co-glycolide) copolymers, methods for making and using same, and devices containing same |
| WO2013098481A1 (en) * | 2011-12-28 | 2013-07-04 | Conmed Linvatec Biomaterials Oy Ltd | Composite containing polymer and additive as well as its use |
| CN115260459A (en) * | 2022-09-02 | 2022-11-01 | 浙江海正生物材料股份有限公司 | Polylactic acid-glycolic acid copolymer and preparation method thereof |
-
2022
- 2022-11-10 CN CN202211402178.XA patent/CN115612072A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050203A (en) * | 1988-08-08 | 1991-03-27 | 巴特尔纪念研究院 | Come from the degradable thermoplastic plastics of rac-Lactide |
| US20030114637A1 (en) * | 2001-09-05 | 2003-06-19 | Sylwester Gogolewski | Poly(L-lactide-co-glycolide) copolymers, methods for making and using same, and devices containing same |
| WO2013098481A1 (en) * | 2011-12-28 | 2013-07-04 | Conmed Linvatec Biomaterials Oy Ltd | Composite containing polymer and additive as well as its use |
| CN115260459A (en) * | 2022-09-02 | 2022-11-01 | 浙江海正生物材料股份有限公司 | Polylactic acid-glycolic acid copolymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| C.A.P.JOZIASS: "Rubber toughened linear and star-shaped poly(d,l-lactide-co-glycolide): synthesis, properties and in vitro degradation", 《POLYMER》, vol. 39, no. 2, pages 467 - 473, XP000992849, DOI: 10.1016/S0032-3861(97)00293-0 * |
| 孙斌，等: "乙交酯、L-丙交酯均聚物及其共聚物的制备和性能研究", 《高分子学报》, no. 9, pages 1274 - 1279 * |
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