CN117247664A - Medical biodegradable transfusion bag film material and preparation method thereof - Google Patents
Medical biodegradable transfusion bag film material and preparation method thereof Download PDFInfo
- Publication number
- CN117247664A CN117247664A CN202311405137.0A CN202311405137A CN117247664A CN 117247664 A CN117247664 A CN 117247664A CN 202311405137 A CN202311405137 A CN 202311405137A CN 117247664 A CN117247664 A CN 117247664A
- Authority
- CN
- China
- Prior art keywords
- film material
- biodegradable
- medical
- bag film
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000004626 polylactic acid Substances 0.000 claims abstract description 55
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 27
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 4
- 229920000071 poly(4-hydroxybutyrate) Polymers 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- 238000001802 infusion Methods 0.000 claims description 25
- 239000000956 alloy Substances 0.000 claims description 24
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 18
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 11
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 10
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 9
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000000071 blow moulding Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 4
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 229940037312 stearamide Drugs 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001069 triethyl citrate Substances 0.000 claims description 4
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000013769 triethyl citrate Nutrition 0.000 claims description 4
- 229940098697 zinc laurate Drugs 0.000 claims description 4
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 229920002988 biodegradable polymer Polymers 0.000 abstract description 6
- 239000004621 biodegradable polymer Substances 0.000 abstract description 6
- 229920000704 biodegradable plastic Polymers 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001816 cooling Methods 0.000 description 9
- 238000010101 extrusion blow moulding Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- AUSGLDHLCBXRML-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 2-[(3-methyloxiran-2-yl)methyl]butanedioate Chemical compound C(C1CO1)OC(=O)CC(CC1C(C)O1)C(=O)OCC1CO1 AUSGLDHLCBXRML-UHFFFAOYSA-N 0.000 description 6
- 238000006065 biodegradation reaction Methods 0.000 description 5
- -1 Polyethylene Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FQKXHBUVYRMIOQ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)(=O)N1N2CCN1N2C(CCCCCCCCCCCCCCCCC)=O Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)N1N2CCN1N2C(CCCCCCCCCCCCCCCCC)=O FQKXHBUVYRMIOQ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a medical biodegradable transfusion bag film material and a preparation method thereof, relating to the technical field of biodegradable plastics; the film material is prepared from the following raw materials in parts by weight: 50-80 parts of polylactic acid; 5-20 parts of biodegradable toughening agent; 0-2 parts of cross-linking agent; 0-20 parts of medical plasticizer; 0-4 parts of a heat stabilizer; 0-0.2 parts of lubricant; 0-0.2 parts of defoaming agent. According to the medical biodegradable transfusion bag film material provided by the invention, the biodegradable polymer material PLA is taken as a main raw material, and the biodegradable toughening agent is combined to toughen and modify the PLA, so that the biodegradable film material meeting the performance requirements of the transfusion bag is obtained.
Description
Technical Field
The invention relates to the technical field of biodegradable plastics, in particular to a medical biodegradable transfusion bag film material and a preparation method thereof.
Background
Infusion therapy is the most common medical mode at present, and an infusion apparatus in infusion therapy is developed from a traditional glass bottle to a polyvinyl chloride (PVC) soft bag, a Polyethylene (PE) and polypropylene (PP) hard plastic bottle until a non-PVC composite film soft bag appears at present. Because of the defects of packaging materials, transfusion modes and the like of the glass transfusion bottle, the conventional transfusion used clinically at present is fully-closed soft bag packaging.
The existing film materials for the infusion bag are mainly PVC materials with relatively low cost, and the materials are gradually replaced by high polymer materials such as polyethylene, polypropylene, ethylene-vinyl acetate (EVA) and the like due to the defect that toxic gases can be generated by combustion due to the fact that the materials cannot be degraded; however, these polymer materials have a problem that it is difficult to carry out biodegradation treatment, and the white pollution is aggravated when used in a large amount.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the problem that a film material for an infusion bag is difficult to biodegrade in the prior art, the invention provides a medical biodegradable infusion bag film material, which takes biodegradable polymer material polylactic acid as a main raw material, and the polylactic acid is toughened and modified by adding a biodegradable toughening agent to obtain the biodegradable film material meeting the performance requirement of the infusion bag, so that the problem that the film material for the infusion bag is difficult to biodegrade in the prior art is solved.
The technical scheme adopted for solving the technical problems is as follows:
a medical biodegradable transfusion bag film material is prepared from the following raw materials in parts by weight:
optionally, the weight average molecular weight of the polylactic acid is 4-80 ten thousand, and the polydispersity is 2-8.
Optionally, the biodegradable toughening agent is polyhydroxybutyrate.
Alternatively, the polyhydroxybutyrate is poly (4-hydroxybutyrate).
Alternatively, the poly (4-hydroxybutyrate) has a weight average molecular weight of 4-20 ten thousand and a polydispersity of 2-6.
Optionally, the cross-linking agent is an epoxy cross-linking agent.
Optionally, the epoxy-based crosslinking agent is a trifunctional epoxy resin.
Optionally, the medical plasticizer is at least one selected from tributyl citrate, triethyl citrate, acetyl tributyl citrate, acetyl triethyl citrate.
Optionally, the heat stabilizer is at least one selected from zinc stearate, zinc laurate, pentaerythritol and sorbitol; the lubricant is at least one selected from ethylenediamine bisstearamide, stearamide and oleamide; the defoamer is at least one selected from methyl silicone oil and tributyl phosphate.
The invention also aims to provide a preparation method of the medical biodegradable transfusion bag film material, which comprises the following steps:
s1: heating and drying polylactic acid and a biodegradable toughening agent to obtain a pretreated raw material;
s2: mixing the pretreated raw materials, a cross-linking agent, a medical plasticizer, a heat stabilizer, a lubricant and a defoaming agent to obtain a premix;
s3: carrying out melt blending, extrusion and granulating on the premix to obtain an alloy material;
s4: and (3) carrying out blow molding on the alloy material to obtain the medical biodegradable transfusion bag film material.
The beneficial effects of the invention are as follows:
according to the medical biodegradable transfusion bag film material provided by the invention, the biodegradable polymer material PLA is taken as a main raw material, and the biodegradable toughening agent is combined to toughen and modify the PLA, so that the biodegradable film material meeting the performance requirements of the transfusion bag is obtained.
Detailed Description
The present invention will now be described in further detail. The embodiments described below are exemplary and intended to illustrate the invention and should not be construed as limiting the invention, as all other embodiments, based on which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of the invention.
In order to solve the problem that the film material for the infusion bag is difficult to biodegrade in the prior art, the invention provides a medical biodegradable infusion bag film material, which is prepared from the following raw materials in parts by weight:
further, the film material is preferably prepared from the following raw materials in parts by weight:
wherein polylactic acid (PLA) is a biodegradable, green and pollution-free polymer material prepared from renewable plants such as corn, cassava and the like; PLA has been widely used in packaging materials, biomedical materials, clothing, agricultural products, electrical appliances and other fields because of its excellent biocompatibility, processability, mechanical properties and other advantages; but PLA has the defects of poor impact strength, low elongation at break and poor toughness, and limits the application of the product; if PLA is directly used for manufacturing the infusion bag, the performance requirement of the infusion bag is difficult to meet; based on this, it is necessary to toughen and modify PLA; in order to ensure the biodegradability of the infusion bag, the biodegradable toughening agent is preferably introduced to toughen and modify PLA, so that the mechanical property of the prepared film material is improved on the premise of ensuring the biodegradability of the film material by the synergistic effect of PLA, the biodegradable toughening agent and other auxiliary agents, and the prepared film material can meet the performance requirement of the infusion bag.
According to the medical biodegradable transfusion bag film material provided by the invention, the biodegradable polymer material PLA is used as the main raw material, the advantages of good biodegradability, biocompatibility, transparency and the like of polylactic acid are utilized, and the biodegradable toughening agent is combined to toughen and modify the PLA, so that the inherent brittleness of the PLA is overcome, and the biodegradable film material meeting the performance requirements of the transfusion bag is obtained.
In order to give consideration to the biodegradability and mechanical properties of the medical biodegradable transfusion bag film material, the weight average molecular weight of the polylactic acid is preferably 4-80 ten thousand, and the polydispersity coefficient is 2-8.
In order to avoid a decrease in PLA strength caused by the addition of a toughening agent, the preferred biodegradable toughening agent of the present invention is polyhydroxybutyrate.
Polyhydroxybutyrate is a biodegradable polymer with excellent biocompatibility, and its degradation products are water and CO, which are completely harmless to the nature and environment 2 Therefore, the introduction of the polyhydroxybutyrate does not affect the biodegradability of the film material and does not pollute the environment; in addition, the polyhydroxybutyrate is nontoxic, does not hydrolyze and is resistant to hydrolytic degradation, has good oxygen permeability and ultraviolet resistance, is used for toughening PLA, and is beneficial to enabling the performance stability of the prepared film material to meet the performance requirements of infusion bags.
In order to ensure that the toughness of PLA is improved without reducing the strength of the material, the polyhydroxybutyrate is preferably poly (4-hydroxybutyrate).
Poly (4-hydroxybutyrate) (P4 HB) is a thermoplastic semi-crystalline material with high strength, good toughness and good processability (low melting point, wide processing temperature and high melt strength); excellent crystallization property, can be completely biodegraded, and the degradation products are water and CO which are completely harmless to the nature and environment 2 The method comprises the steps of carrying out a first treatment on the surface of the The biological compatibility is good, and the degradation products are fast metabolized; therefore, the film material can be used for preparing the film material meeting the performance requirements of the infusion bag through extrusion, injection molding, foaming, blow molding, thermoforming and other processes under the synergistic effect of PLA.
Further, in order to achieve both the mechanical properties and biodegradability of the film material, the poly (4-hydroxybutyrate) of the present invention preferably has a weight average molecular weight of 4-20 ten thousand and a polydispersity of 2-6.
In order to improve the compatibility between the polylactic acid and the biodegradable toughening agent, the invention preferably adds a cross-linking agent into the system; furthermore, the cross-linking agent is preferably an epoxy cross-linking agent, so that the compatibility of the polylactic acid and the poly (4-hydroxybutyrate) is improved and the toughness is further improved through the slight cross-linking chemical reaction between the epoxy group and the hydroxyl or carboxyl at the tail ends of the polylactic acid and the poly (4-hydroxybutyrate).
Further, the epoxy-based crosslinking agent of the present invention is preferably a trifunctional epoxy resin, and particularly preferably diglycidyl 4, 5-epoxyhexane-1, 2-dicarboxylate.
In order to improve the processing performance, the invention further introduces proper medical plasticizers, heat stabilizers, lubricants, defoamers and other assistants into the system, so that the medical biodegradable transfusion bag film material can be obtained after melt blending, extrusion, granulating and blow molding, and is used as a disposable medical transfusion bag.
In particular, the medical plasticizer is preferably at least one selected from tributyl citrate, triethyl citrate, acetyl tributyl citrate and acetyl triethyl citrate; preferably, the heat stabilizer is at least one selected from zinc stearate, zinc laurate, pentaerythritol and sorbitol; the lubricant is at least one of ethylenediamine bisstearamide, stearamide and oleamide; the defoamer is at least one selected from methyl silicone oil and tributyl phosphate.
The invention utilizes the advantages of good biodegradability, biocompatibility, transparency and the like of polylactic acid, simultaneously, in order to overcome the inherent brittleness, poly (4-hydroxybutyrate) with biodegradability, biocompatibility and good toughness is added for blending and toughening, then a proper amount of epoxy cross-linking agent is added, and the epoxy group and hydroxyl or carboxyl at the tail end of the polylactic acid and the poly (4-hydroxybutyrate) undergo slight cross-linking chemical reaction, so that the compatibility of the polylactic acid and the poly (4-hydroxybutyrate) is improved, the toughness is further improved, and meanwhile, the proper auxiliary agents such as plasticizer, heat stabilizer, lubricant, defoamer and the like are added, the processability is improved, and the film material of the medical biodegradable transfusion bag is hopefully obtained through melt blending, extrusion, granulating and blow molding.
Another object of the present invention is to provide a method for preparing the medical biodegradable transfusion bag film material as described above, comprising the steps of:
s1: heating and drying polylactic acid and a biodegradable toughening agent to obtain a pretreated raw material;
s2: mixing the pretreated raw materials, a cross-linking agent, a medical plasticizer, a heat stabilizer, a lubricant and a defoaming agent to obtain a premix;
s3: carrying out melt blending, extrusion and granulating on the premix to obtain an alloy material;
s4: and (3) carrying out blow molding on the alloy material to obtain the medical biodegradable transfusion bag film material.
According to the preparation method of the medical biodegradable transfusion bag film material, the biodegradable polymer material PLA is taken as a main raw material, and the biodegradable toughening agent is combined to toughen and modify the PLA, so that the biodegradable film material meeting the performance requirements of the transfusion bag is obtained.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Example 1
The embodiment provides a preparation method of a medical biodegradable transfusion bag film material, wherein the weight average molecular weight of polylactic acid is 200000, and the distribution coefficient is 3.5; the weight average molecular weight of poly (4-hydroxybutyrate) was 93000 and the distribution coefficient was 4.2.
The preparation method comprises the following steps:
s1: according to parts by weight, 70 parts by weight of polylactic acid and 15 parts by weight of poly (4-hydroxybutyrate) are heated and dried at 70 ℃ for 6 hours to obtain a pretreated raw material;
s2: adding the pretreated raw materials, 1 part by weight of cross-linking agent 4, 5-epoxyhexane-1, 2-dicarboxylic acid diglycidyl ester, 10 parts by weight of tributyl citrate, 2 parts by weight of zinc stearate, 0.1 part by weight of ethylenediamine bisstearamide and 0.1 part by weight of methyl silicone oil into a high-speed mixer, and mixing for 10 minutes at a rotation speed of 400rpm to obtain a premix;
s3: adding the obtained premix into a double-screw extruder for melt blending, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃, setting the temperature of the die to be 180 ℃ and setting the rotating speed of a screw to be 140rpm; extruding, cooling and granulating the blend through a die to obtain an alloy material;
s4: and adding the obtained alloy material into a single screw extruder for extrusion blow molding, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃ and setting the temperature of the die to be 180 ℃ to obtain the medical biodegradable transfusion bag film material.
Example 2
The embodiment provides a preparation method of a medical biodegradable transfusion bag film material, wherein the weight average molecular weight of polylactic acid is 200000, and the distribution coefficient is 3.5; the weight average molecular weight of poly (4-hydroxybutyrate) was 93000 and the distribution coefficient was 4.2.
The preparation method comprises the following steps:
s1: according to parts by weight, 60 parts by weight of polylactic acid and 10 parts by weight of poly (4-hydroxybutyrate) are heated and dried at 70 ℃ for 6 hours to obtain a pretreated raw material;
s2: adding the pretreated raw materials, 0.5 weight part of cross-linking agent 4, 5-epoxyhexane-1, 2-diglycidyl ester, 8 weight parts of triethyl citrate, 1.5 weight parts of zinc laurate, 0.1 weight part of ethylenediamine bisstearamide and 0.1 weight part of methyl silicone oil into a high-speed stirrer, and mixing for 10 minutes at a rotation speed of 400rpm to obtain a premix;
s3: adding the obtained premix into a double-screw extruder for melt blending, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃, setting the temperature of the die to be 180 ℃ and setting the rotating speed of a screw to be 140rpm; extruding, cooling and granulating the blend through a die to obtain an alloy material;
s4: and adding the obtained alloy material into a single screw extruder for extrusion blow molding, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃ and setting the temperature of the die to be 180 ℃ to obtain the medical biodegradable transfusion bag film material.
Example 3
The embodiment provides a preparation method of a medical biodegradable transfusion bag film material, wherein the weight average molecular weight of polylactic acid is 200000, and the distribution coefficient is 3.5; the weight average molecular weight of poly (4-hydroxybutyrate) was 93000 and the distribution coefficient was 4.2.
The preparation method comprises the following steps:
s1: according to parts by weight, 50 parts by weight of polylactic acid and 5 parts by weight of poly (4-hydroxybutyrate) are heated and dried at 70 ℃ for 6 hours to obtain a pretreated raw material;
s2: adding the pretreated raw materials, 0.5 part by weight of cross-linking agent 4, 5-epoxyhexane-1, 2-diglycidyl ester, 5 parts by weight of acetyl tributyl citrate, 1 part by weight of zinc stearate, 0.1 part by weight of stearamide and 0.1 part by weight of methyl silicone oil into a high-speed mixer, and mixing for 10 minutes at a rotation speed of 400rpm to obtain a premix;
s3: adding the obtained premix into a double-screw extruder for melt blending, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃, setting the temperature of the die to be 180 ℃ and setting the rotating speed of a screw to be 140rpm; extruding, cooling and granulating the blend through a die to obtain an alloy material;
s4: and adding the obtained alloy material into a single screw extruder for extrusion blow molding, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃ and setting the temperature of the die to be 180 ℃ to obtain the medical biodegradable transfusion bag film material.
Example 4
The embodiment provides a preparation method of a medical biodegradable transfusion bag film material, wherein the weight average molecular weight of polylactic acid is 200000, and the distribution coefficient is 3.5; the weight average molecular weight of poly (4-hydroxybutyrate) was 93000 and the distribution coefficient was 4.2.
The preparation method comprises the following steps:
s1: according to parts by weight, 80 parts by weight of polylactic acid and 20 parts by weight of poly (4-hydroxybutyrate) are heated and dried at 70 ℃ for 6 hours to obtain a pretreated raw material;
s2: adding the pretreated raw materials, 2 parts by weight of cross-linking agent 4, 5-epoxyhexane-1, 2-dicarboxylic acid diglycidyl ester, 20 parts by weight of acetyl triethyl citrate, 1 part by weight of zinc stearate, 0.1 part by weight of ethylenediamine bisstearamide and 0.1 part by weight of tributyl phosphate into a high-speed mixer, and mixing for 10 minutes at a rotation speed of 400rpm to obtain a premix;
s3: adding the obtained premix into a double-screw extruder for melt blending, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃, setting the temperature of the die to be 180 ℃ and setting the rotating speed of a screw to be 140rpm; extruding, cooling and granulating the blend through a die to obtain an alloy material;
s4: and adding the obtained alloy material into a single screw extruder for extrusion blow molding, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃ and setting the temperature of the die to be 180 ℃ to obtain the medical biodegradable transfusion bag film material.
Example 5
The difference between this example and example 1 is that the polylactic acid has a weight average molecular weight of 50000 and a distribution coefficient of 2.5; the weight average molecular weight of poly (4-hydroxybutyrate) was 46000 and the distribution coefficient was 3.0.
Comparative example 1
The comparative example provides a method for preparing a film material, wherein the weight average molecular weight of polylactic acid is 200000 and the distribution coefficient is 3.5.
The preparation method comprises the following steps:
s1: according to parts by weight, 85 parts by weight of polylactic acid is heated and dried at 70 ℃ for 6 hours to obtain a pretreated raw material;
s2: adding the pretreated raw materials, 1 part by weight of cross-linking agent 4, 5-epoxyhexane-1, 2-dicarboxylic acid diglycidyl ester, 10 parts by weight of tributyl citrate, 2 parts by weight of zinc stearate, 0.1 part by weight of ethylenediamine bisstearamide and 0.1 part by weight of methyl silicone oil into a high-speed mixer, and mixing for 10 minutes at a rotation speed of 400rpm to obtain a premix;
s3: adding the obtained premix into a double-screw extruder for melt blending, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃, setting the temperature of the die to be 180 ℃ and setting the rotating speed of a screw to be 140rpm; extruding, cooling and granulating the blend through a die to obtain an alloy material;
s4: and adding the obtained alloy material into a single screw extruder for extrusion blow molding, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃ and setting the temperature of the die to be 180 ℃ to obtain the medical biodegradable transfusion bag film material.
Comparative example 2
The comparative example provides a method for preparing a film material, wherein the weight average molecular weight of polylactic acid is 200000, and the distribution coefficient is 3.5; the weight average molecular weight of poly (4-hydroxybutyrate) was 250000 and the distribution coefficient was 4.2.
The preparation method comprises the following steps:
s1: according to parts by weight, 70 parts by weight of polylactic acid and 15 parts by weight of poly (4-hydroxybutyrate) are heated and dried at 70 ℃ for 6 hours to obtain a pretreated raw material;
s2: adding the pretreated raw materials, 1 part by weight of cross-linking agent 4, 5-epoxyhexane-1, 2-dicarboxylic acid diglycidyl ester, 10 parts by weight of tributyl citrate, 2 parts by weight of zinc stearate, 0.1 part by weight of ethylenediamine bisstearamide and 0.1 part by weight of methyl silicone oil into a high-speed mixer, and mixing for 10 minutes at a rotation speed of 400rpm to obtain a premix;
s3: adding the obtained premix into a double-screw extruder for melt blending, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃, setting the temperature of the die to be 180 ℃ and setting the rotating speed of a screw to be 140rpm; extruding, cooling and granulating the blend through a die to obtain an alloy material;
s4: and adding the obtained alloy material into a single screw extruder for extrusion blow molding, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃ and setting the temperature of the die to be 180 ℃ to obtain the medical biodegradable transfusion bag film material.
Comparative example 3
The comparative example provides a method for preparing a film material, wherein the weight average molecular weight of polylactic acid is 200000 and the distribution coefficient is 3.5.
The preparation method comprises the following steps:
s1: according to parts by weight, 70 parts by weight of polylactic acid and 15 parts by weight of polycaprolactone are heated and dried at 70 ℃ for 6 hours to obtain a pretreated raw material;
s2: adding the pretreated raw materials, 1 part by weight of cross-linking agent 4, 5-epoxyhexane-1, 2-dicarboxylic acid diglycidyl ester, 10 parts by weight of tributyl citrate, 2 parts by weight of zinc stearate, 0.1 part by weight of ethylenediamine bisstearamide and 0.1 part by weight of methyl silicone oil into a high-speed mixer, and mixing for 10 minutes at a rotation speed of 400rpm to obtain a premix;
s3: adding the obtained premix into a double-screw extruder for melt blending, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃, setting the temperature of the die to be 180 ℃ and setting the rotating speed of a screw to be 140rpm; extruding, cooling and granulating the blend through a die to obtain an alloy material;
s4: and adding the obtained alloy material into a single screw extruder for extrusion blow molding, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃ and setting the temperature of the die to be 180 ℃ to obtain the medical biodegradable transfusion bag film material.
Comparative example 4
The comparative example provides a method for preparing a film material, wherein the weight average molecular weight of polylactic acid is 200000, and the distribution coefficient is 3.5; the weight average molecular weight of poly (4-hydroxybutyrate) was 93000 and the distribution coefficient was 4.2.
The preparation method comprises the following steps:
s1: according to parts by weight, 70 parts by weight of polylactic acid and 15 parts by weight of poly (4-hydroxybutyrate) are heated and dried at 70 ℃ for 6 hours to obtain a pretreated raw material;
s2: adding the pretreated raw materials, 10 parts by weight of tributyl citrate, 2 parts by weight of zinc stearate, 0.1 part by weight of ethylenediamine bisstearamide and 0.1 part by weight of methyl silicone oil into a high-speed stirrer, and mixing for 10 minutes at a rotating speed of 400rpm to obtain a premix;
s3: adding the obtained premix into a double-screw extruder for melt blending, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃, setting the temperature of the die to be 180 ℃ and setting the rotating speed of a screw to be 140rpm; extruding, cooling and granulating the blend through a die to obtain an alloy material;
s4: and adding the obtained alloy material into a single screw extruder for extrusion blow molding, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃ and setting the temperature of the die to be 180 ℃ to obtain the medical biodegradable transfusion bag film material.
Comparative example 5
The comparative example provides a method for preparing a film material, wherein the weight average molecular weight of polylactic acid is 200000, and the distribution coefficient is 3.5; the weight average molecular weight of poly (4-hydroxybutyrate) was 93000 and the distribution coefficient was 4.2.
The preparation method comprises the following steps:
s1: according to parts by weight, 70 parts by weight of polylactic acid and 15 parts by weight of poly (4-hydroxybutyrate) are heated and dried at 70 ℃ for 6 hours to obtain a pretreated raw material;
s2: adding the pretreated raw materials, 1 part by weight of triallyl isocyanurate serving as a crosslinking agent, 10 parts by weight of tributyl citrate, 2 parts by weight of zinc stearate, 0.1 part by weight of ethylenediamine distearamide and 0.1 part by weight of methyl silicone oil into a high-speed stirrer, and mixing for 10 minutes at a rotating speed of 400rpm to obtain a premix;
s3: adding the obtained premix into a double-screw extruder for melt blending, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃, setting the temperature of the die to be 180 ℃ and setting the rotating speed of a screw to be 140rpm; extruding, cooling and granulating the blend through a die to obtain an alloy material;
s4: and adding the obtained alloy material into a single screw extruder for extrusion blow molding, setting the temperature from a feed inlet of the extruder to the direction of a die to be 150-220 ℃ and setting the temperature of the die to be 180 ℃ to obtain the medical biodegradable transfusion bag film material.
The film materials prepared in the above examples and comparative examples were subjected to performance testing as follows:
mechanical property test: testing is performed with reference to GB/T1040.3-2006;
transmittance: testing with reference to GB/T2410-2008;
oxygen transmission amount: testing with reference to GB/T1038-2000;
relative biodegradation rate (180 days): the test was performed with reference to GB/T19277.1.
The test results are shown in Table 1:
TABLE 1
As can be seen from the data in the table above, the film materials prepared in the examples of the present invention all have excellent longitudinal tensile strength and transverse tensile strength, and elongation at break; low oxygen transmission, indicating excellent barrier properties; the light transmittance is above 90%, and the transparent glass has excellent transparency; has very high relative biological decomposition rate, good barrier property and good mechanical property; the result shows that the medical biodegradable transfusion bag film material is suitable for being used as a disposable medical transfusion bag.
The difference between comparative example 1 and example 1 is that poly (4-hydroxybutyrate) is not added, and the prepared film material has higher relative biological decomposition rate, but the elongation at break is obviously reduced compared with example 1, and the mechanical property of the film material can not meet the performance requirement of a disposable medical infusion bag.
The difference between comparative example 2 and example 1 is that the weight average molecular weight of poly (4-hydroxybutyrate) is 250000, and the prepared film material has low tensile strength and elongation at break, and the relative biodegradation rate is reduced, so that the comprehensive performance of the film material is reduced, and the performance requirement of the disposable medical infusion bag cannot be met.
The difference between comparative example 3 and example 1 is that polycaprolactone is used for replacing poly (4-hydroxybutyrate), and the elongation at break of the prepared film material is obviously improved compared with comparative example 1, but still lower than example 1, and the mechanical property of the film material still cannot meet the performance requirement of the disposable medical infusion bag.
The difference between comparative example 4 and example 1 is that the prepared film material is lower in tensile strength and elongation at break than example 1 without adding epoxy cross-linking agent, and the relative biodegradation rate is reduced, so that the comprehensive performance of the film material is reduced, and the performance requirement of the disposable medical infusion bag cannot be met.
The difference between comparative example 5 and example 1 is that the triallyl isocyanurate as a crosslinking agent is used for replacing the epoxy crosslinking agent, the elongation at break and the tensile strength of the prepared film material are lower than those of the film material added with the epoxy crosslinking agent, and the relative biodegradation rate is also reduced, so that the comprehensive performance of the film material is reduced, and the performance requirement of the disposable medical infusion bag cannot be met.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (10)
1. The medical biodegradable transfusion bag film material is characterized by being prepared from the following raw materials in parts by weight:
2. the medical biodegradable transfusion bag film material according to claim 1, characterized in that said polylactic acid has a weight average molecular weight of 4-80 ten thousand and a polydispersity of 2-8.
3. The medical biodegradable infusion bag film material according to claim 1, characterized in that said biodegradable toughening agent is polyhydroxybutyrate.
4. The medical biodegradable infusion bag film material according to claim 3, characterized in that said polyhydroxybutyrate is poly (4-hydroxybutyrate).
5. The medical biodegradable transfusion bag film material according to claim 4, wherein said poly (4-hydroxybutyrate) has a weight average molecular weight of 4-20 ten thousand and a polydispersity of 2-6.
6. The medical biodegradable transfusion bag film material according to any one of claims 1-5, characterized in that said crosslinking agent is an epoxy crosslinking agent.
7. The medical biodegradable transfusion bag film material according to claim 6, wherein said epoxy cross-linking agent is a trifunctional epoxy resin.
8. The medical biodegradable infusion bag film material according to any one of claims 1-5, characterized in that said medical plasticizer is selected from at least one of tributyl citrate, triethyl citrate, acetyl tributyl citrate, acetyl triethyl citrate.
9. The medical biodegradable infusion bag film material according to any one of claims 1-5, characterized in that said heat stabilizer is selected from at least one of zinc stearate, zinc laurate, pentaerythritol, sorbitol; the lubricant is at least one selected from ethylenediamine bisstearamide, stearamide and oleamide; the defoamer is at least one selected from methyl silicone oil and tributyl phosphate.
10. A method for preparing a medical biodegradable transfusion bag film material as set forth in any one of claims 1 to 9, characterized by comprising the steps of:
s1: heating and drying polylactic acid and a biodegradable toughening agent to obtain a pretreated raw material;
s2: mixing the pretreated raw materials, a cross-linking agent, a medical plasticizer, a heat stabilizer, a lubricant and a defoaming agent to obtain a premix;
s3: carrying out melt blending, extrusion and granulating on the premix to obtain an alloy material;
s4: and (3) carrying out blow molding on the alloy material to obtain the medical biodegradable transfusion bag film material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311405137.0A CN117247664A (en) | 2023-10-27 | 2023-10-27 | Medical biodegradable transfusion bag film material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311405137.0A CN117247664A (en) | 2023-10-27 | 2023-10-27 | Medical biodegradable transfusion bag film material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117247664A true CN117247664A (en) | 2023-12-19 |
Family
ID=89133216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311405137.0A Pending CN117247664A (en) | 2023-10-27 | 2023-10-27 | Medical biodegradable transfusion bag film material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117247664A (en) |
-
2023
- 2023-10-27 CN CN202311405137.0A patent/CN117247664A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108822514B (en) | Completely biodegradable polylactic acid based blown film and preparation method thereof | |
| CN111040400A (en) | Full-biodegradable sheet and preparation method thereof | |
| CN112552654B (en) | PBAT/PHA/wood flour composition suitable for preparing film and preparation and application thereof | |
| CN113956623B (en) | Full-biodegradable plastic composite modified material suitable for film bag and preparation method thereof | |
| CN104387732A (en) | Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof | |
| CN111205604B (en) | Ultrathin high-strength high-toughness biodegradable mulch film material, film, preparation method and application | |
| CN113956630A (en) | Completely biodegradable film and preparation method thereof | |
| CN111662539A (en) | Biodegradable bubble bag material and preparation method thereof | |
| CN112500611B (en) | Biodegradable plastic bag and preparation method thereof | |
| CN108017887A (en) | A kind of PLA-PBSA inflation films and preparation method thereof | |
| CN113045881A (en) | Thermal-shrinkage degradable environment-friendly film material and preparation method and application method thereof | |
| CN112694726A (en) | Modified PGA material with higher processing performance and preparation method thereof | |
| CN113956627A (en) | Precipitation-resistant and low-haze starch-based fully biodegradable PBAT alloy and preparation method thereof | |
| CN106397842A (en) | Packaging film material with degradability | |
| CN110423338B (en) | Preparation method of modified polylactic acid material | |
| CN115433441A (en) | Full-biodegradable material and preparation method thereof | |
| CN111849130A (en) | Full-biodegradable plastic film and preparation method thereof | |
| CN111907031A (en) | PLA/PBAT film, preparation method and application | |
| CN113185818B (en) | Biodegradable polylactic acid high-transparency film and preparation method thereof | |
| CN113150395B (en) | Thermoplastic starch with ultrahigh starch content, and preparation method and application thereof | |
| CN114407471A (en) | Three-layer co-extrusion biodegradable automatic packaging film material and manufacturing method thereof | |
| WO2021112397A1 (en) | Biodegradable resin composition and method for producing same | |
| CN112322001A (en) | Impact-resistant modified PET plastic and preparation method thereof | |
| CN117247664A (en) | Medical biodegradable transfusion bag film material and preparation method thereof | |
| CN113831702A (en) | Degradable plastic lunch box composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |