CN113789039A - Biodegradable polyester heat shrinkable film and preparation method thereof - Google Patents
Biodegradable polyester heat shrinkable film and preparation method thereof Download PDFInfo
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- CN113789039A CN113789039A CN202111151918.2A CN202111151918A CN113789039A CN 113789039 A CN113789039 A CN 113789039A CN 202111151918 A CN202111151918 A CN 202111151918A CN 113789039 A CN113789039 A CN 113789039A
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- heat shrinkable
- shrinkable film
- biodegradable polyester
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- 229920006257 Heat-shrinkable film Polymers 0.000 title claims abstract description 37
- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 20
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 14
- 238000010894 electron beam technology Methods 0.000 claims abstract description 13
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 230000002457 bidirectional effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 23
- 239000000344 soap Substances 0.000 claims description 21
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000004970 Chain extender Substances 0.000 claims description 13
- 239000012760 heat stabilizer Substances 0.000 claims description 12
- 150000002148 esters Chemical group 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 8
- 239000000155 melt Substances 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 238000009998 heat setting Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ROZZMLUWBPPEMU-GRVYQHKQSA-L Calcium linoleate Chemical compound [Ca+2].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O ROZZMLUWBPPEMU-GRVYQHKQSA-L 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- ZCZLQYAECBEUBH-UHFFFAOYSA-L calcium;octadec-9-enoate Chemical compound [Ca+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O ZCZLQYAECBEUBH-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 229940012185 zinc palmitate Drugs 0.000 claims description 3
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 claims description 3
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 claims description 3
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- SEOKMRXFVOVAIL-UHFFFAOYSA-L barium(2+);terephthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 SEOKMRXFVOVAIL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 14
- 230000004888 barrier function Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 239000004626 polylactic acid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005809 transesterification reaction Methods 0.000 description 7
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- HRBZRZSCMANEHQ-UHFFFAOYSA-L calcium;hexadecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O HRBZRZSCMANEHQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 238000009966 trimming Methods 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
-
- 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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention relates to a biodegradable polyester heat shrinkable film which is prepared from the following raw materials in parts by weight: 40-50 parts of PLA, 30-40 parts of PBAT, 15-30 parts of function-adjusting degradable master batch, 5-10 parts of compatilizer, 6-12 parts of plasticizer, 1-3 parts of slipping agent and 0.5-1 part of anti-aging agent. Compared with the prior art, the preparation process has good stability, the obtained bidirectional oriented film is subjected to electron beam irradiation at the later stage of the process, so that polyester molecular chains in a base material can be subjected to micro-crosslinking to a certain degree, the improvement of the heat shrinkage performance of the film is facilitated, the water vapor barrier performance and the mechanical property of the film are also facilitated, the electron beam irradiation process is pollution-free, the treatment efficiency is high, the prepared heat shrinkage film can be completely degraded within a certain time, and the preparation method is green and environment-friendly and can be widely applied to the packaging fields of foods, daily necessities, electronic products, electronic devices and the like.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a biodegradable polyester heat shrinkable film and a preparation method thereof.
Background
Among a plurality of film products, the heat shrinkable film is a film with higher puncture resistance, good shrinkability and certain shrinkage stress, and has the main characteristic that the film can shrink under the heating condition, when the film is used for stabilizing, covering and protecting products, the heat shrinkable film can show the appearance of the packaged objects to play a role in beauty, or the packaged objects can be integrated to facilitate the circulation of the objects, and the film also has the functions of moisture prevention, dust prevention and the like. The production principle of the heat shrinkable film is that a preformed polymer film is stretched in the temperature range of above the softening point and below the melting point of a base resin to orient molecular chains in the base resin, then the preformed polymer film is rapidly cooled to freeze the oriented molecular chains, when the heat shrinkable film is used, the film can be reheated, the molecular chains in the base resin are converted to an unoriented state by virtue of the self-recovery action of the molecular chains, and the size of the film is gradually shortened in the process from the macroscopic view, so that the shrinking effect is realized.
In the prior art, materials used for preparing the heat shrinkable film are mainly polyethylene, polypropylene, polyvinyl chloride, polyester (for example, polyethylene terephthalate) and the like, but the materials are difficult to naturally degrade, and since the market demand of the heat shrinkable film is increased at a remarkable rate and the amount of the heat shrinkable film used is large every year, a large amount of plastic waste is generated, and environmental pollution is caused, there is a great need to develop a heat shrinkable film which is green and environment-friendly and can basically realize full biodegradation.
Currently, relatively few studies are made on biodegradable heat shrinkable films, and heat shrinkable films prepared based on biodegradable materials generally have disadvantages of low toughness and strength, poor heat shrinkability, and the like, for example, polylactic acid used as a material for preparing heat shrinkable films is itself brittle and has problems of low melt strength, poor water vapor barrier property, and to-be-improved heat shrinkability.
Disclosure of Invention
An object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a biodegradable polyester heat shrinkable film having good toughness, good molding stability, and good heat shrinkability and water vapor barrier properties.
The invention also aims to provide a preparation method of the biodegradable polyester heat shrinkable film.
The purpose of the invention can be realized by the following technical scheme:
according to one aspect of the invention, the biodegradable polyester heat shrinkable film is prepared from the following raw materials in parts by weight: 40-50 parts of PLA, 30-40 parts of PBAT, 15-30 parts of function-adjusting degradable master batch, 5-10 parts of compatilizer, 6-12 parts of plasticizer, 1-3 parts of slipping agent and 0.5-1 part of anti-aging agent.
Preferably, the weight average molecular weight of the PLA and the PBAT is not less than 6 ten thousand.
As an embodiment, the function-adjusting degradable master batch is prepared from the following raw materials in parts by weight: 70-90 parts of PLGA, 10-30 parts of PGA, 0.5-2 parts of ester exchange catalyst, 0.1-0.6 part of heat stabilizer and 0.5-1.5 parts of chain extender.
In one embodiment, the PLGA has a weight average molecular weight of 3 to 6 ten thousand and a GA repeating unit content of 10 to 40 mol% in the molecular chain.
As an embodiment, the transesterification catalyst is one or both of tetrabutyl titanate or tetraisopropyl titanate.
As an embodiment, the heat stabilizer is selected from one or more of calcium stearate soap, calcium oleate soap, calcium palmitoleate soap, calcium linoleate soap, zinc stearate soap, zinc palmitate soap and zinc oleate soap.
As an embodiment, the chain extender is one or more of ADR4380, ADR4385 and ADR4400 which are commercially available.
As an embodiment, the preparation method of the function-adjusting degradable master batch comprises the following steps:
s1: mixing PLGA, PGA and an ester exchange catalyst according to the weight part, then melting and blending at 220-230 ℃, and then extruding and granulating to prepare premixed master batch;
s2: and melting and blending the premixed master batch, the chain extender and the heat stabilizer at the temperature of 180-200 ℃, and then extruding and granulating to obtain the functional adjustment degradable master batch.
As an embodiment, the compatibilizer is glycidyl methacrylate grafted PLA having a melt index of 8 to 12g/10min (190 ℃,2.16kg) and a glycidyl methacrylate graft ratio of 0.61 to 1.02%.
As an embodiment, the plasticizer is prepared by mixing epoxidized soybean oil and pentaerythritol in a mass ratio of 2-4: 1.
As an embodiment, the slipping agent is formed by mixing erucamide and ethylene bis stearamide according to the mass ratio of 1-5: 1.
In one embodiment, the anti-aging agent is a mixture of 2- (2H-benzotriazole-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol and barium terephthalate in a mass ratio of 1-3: 1.
According to another aspect of the present invention, there is provided a method for preparing the biodegradable polyester heat shrinkable film, comprising the steps of:
step 1: adding the components into a double-screw extruder according to the parts by weight, heating, melting and blending, extruding by a die head of the double-screw extruder, attaching the extruded melt to the surface of a casting roller, and cooling to obtain a cast sheet;
step 2: carrying out biaxial stretching on the obtained cast sheet, and then carrying out heat setting to obtain a biaxial orientation film;
and step 3: and (3) performing electron beam irradiation on the prepared bidirectional oriented film, and then performing edge cutting and rolling to obtain the biodegradable polyester heat shrinkable film.
As an embodiment, the temperature of the melt blending in the step 1 is 190-210 ℃, the die head temperature of the double-screw extruder is 210-220 ℃, and the temperature of the casting roll is 30-60 ℃.
As an embodiment, the biaxial stretching in the step 2 is longitudinal stretching and transverse stretching, the temperature of the biaxial stretching is controlled to be 70-90 ℃, the stretching speed is controlled to be 50-100mm/s, the stretching ratio is 3-5, and the temperature of the heat setting is 120-150 ℃.
As an embodiment, the electron beam irradiation in step 3 is performed in an inert gas atmosphere, and the irradiation dose is 100-150 kGy.
Compared with the prior art, the invention has the following characteristics:
1) the heat shrinkable film takes PLA and PBAT as main base materials, the rigidity of the PLA is reduced by using PBAT so as to endow the base materials with good flexibility, glycidyl methacrylate grafted PLA is taken as a compatilizer, wherein glycidyl methacrylate grafted on a PLA main chain can form a strong function with a PBAT molecular chain, so that the interfacial tension between the PBAT and the PLA can be reduced, and the compatibility between the PLA and the PBAT can be obviously improved;
2) the film material system of the invention also introduces the function-adjusting degradable master batch which is formed by melt blending and compounding PLGA and PGA, ester exchange reaction can be generated in the melt blending process by controlling the addition amount of an ester exchange catalyst, so as to flexibly regulate and control the content of GA repeating units (i.e. glycolic acid repeating units) in the PLGA, and the orientation movement capability of molecular chains of the GA repeating units is better than that of molecular chains of LA repeating units (i.e. lactic acid repeating units), therefore, the introduction of the function-adjusting degradable master batch is beneficial to improving the orientation movement capability of the molecular chains of the base material, so that the film material has good heat shrinkage, in addition, electron beam irradiation is carried out at the later stage of film forming processing, the glycidyl methacrylate grafted PLA can also generate a certain degree of cross-linking bonding effect with the PLGA and the PGA in the master batch, and the shrinkage of the film under the heating condition is also beneficial to increase, reducing the shrinkage force during heat shrinkage;
3) the preparation process has good stability, the obtained bidirectional oriented film is subjected to electron beam irradiation at the later stage of the process, so that polyester molecular chains in a base material can be subjected to micro-crosslinking to a certain degree, the improvement of the heat shrinkage performance of the film is facilitated, the water vapor barrier performance and the mechanical property of the film are also facilitated, the electron beam irradiation process is pollution-free, the treatment efficiency is high, the prepared heat shrinkage film can be completely degraded within a certain time, the method is green and environment-friendly, and the method can be widely applied to the packaging fields of food, daily necessities, electronic products, electronic devices and the like and has good application prospects.
Detailed Description
The heat shrinkable film takes PLA and PBAT as main base materials, and the introduction of the glycidyl methacrylate grafted PLA is used for improving the compatibility between the PLA and the PBAT, and the grafted glycidyl methacrylate can also generate a certain degree of cross-linking bonding effect with the PLA and the PBAT in the base materials in the subsequent electron beam irradiation, so that the heat shrinkable film is not only beneficial to improving the barrier effect of the base materials on water vapor, but also beneficial to improving the mechanical strength and the aging resistance of the base materials; in addition, a function-adjusting degradable master batch is introduced into a material system, the function-adjusting degradable master batch is formed by melt blending PLGA and PGA, ester exchange reaction can be carried out in the melt blending process by controlling the addition amount of an ester exchange catalyst, so that the content of GA repeating units (namely glycolic acid repeating units) in the PLGA can be flexibly regulated and controlled, and the orientation movement capability of molecular chains of the GA repeating units is better than that of molecular chains of LA repeating units (namely lactic acid repeating units), so that the introduction of the function-adjusting degradable master batch is beneficial to improving the orientation movement capability of the molecular chains of a base material, the film material has good heat shrinkage, and the introduction of the function-adjusting degradable master batch is beneficial to reducing the shrinkage force in the heat shrinkage process.
Based on this, the present invention has been completed.
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
As used herein, the term "about" when used to modify a numerical value means within + -5% of the error margin measured for that value.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism. The present invention will be described in detail with reference to specific examples.
Specific examples 1 to 5 are given below, wherein the components contained and their contents in parts by weight are shown in the following tables 1 to 1.
TABLE 1-1 raw material components and their parts by weight contents
| Item | PLA | PBAT | Function-adjusting degradable master batch | Compatilizer | Plasticizer | Slipping agent | Anti-aging agent |
| Example 1 | 40 | 30 | 30 | 10 | 6 | 1 | 0.5 |
| Example 2 | 42 | 40 | 18 | 10 | 8 | 1 | 0.5 |
| Example 3 | 45 | 30 | 25 | 8 | 10 | 2 | 0.7 |
| Example 4 | 48 | 32 | 20 | 6 | 10 | 3 | 0.7 |
| Example 5 | 50 | 35 | 15 | 5 | 12 | 3 | 1 |
Note: the weight average molecular weight of PLA in table 1 above was about 8.6 ten thousand, and the weight average molecular weight of PBAT was about 7.2 ten thousand.
Specific information on the compatibilizer, plasticizer, slipping agent and anti-aging agent used in the raw material components of examples 1 to 5 is shown in the following tables 1 to 2.
TABLE 1-2 details of the relevant feed Components
The raw material components and the weight part contents of the function-adjusting degradable master batch used in the above examples 1 to 5 are shown in the following table 2.
Table 2 raw material components and their weight parts contents
| Item | PLGA | PGA | Transesterification catalysts | Heat stabilizer | Chain extender |
| Example 1 | 70 | 30 | 0.5 | 0.1 | 0.5 |
| Example 2 | 74 | 26 | 0.9 | 0.4 | 0.8 |
| Example 3 | 80 | 20 | 1.2 | 0.5 | 1.0 |
| Example 4 | 83 | 17 | 1.5 | 0.5 | 1.2 |
| Example 5 | 90 | 10 | 2.0 | 0.6 | 1.5 |
In the above table 2, specific information on each raw material component is as follows:
the weight average molecular weight of PLGA used in example 1 was about 3.2 ten thousand, the mole percentage content of GA repeat units in the molecular chain was about 10%, the weight average molecular weight of PGA used was about 5.1 ten thousand, the transesterification catalyst used was tetrabutyl titanate, the heat stabilizer used was calcium stearate soap, and the chain extender used was commercially available ADR 4380.
Example 2 used PLGA having a weight average molecular weight of about 4.4 ten thousand and a GA repeat unit mole percentage content in the molecular chain of about 24%, PGA having a weight average molecular weight of about 5.1 ten thousand, a transesterification catalyst of tetraisopropyl titanate, a thermal stabilizer of calcium oleate soap, and a chain extender of commercially available ADR 4385.
Example 3 the weight average molecular weight of PLGA used was about 4.9 ten thousand, the mole percentage content of GA repeat units in the molecular chain was about 30%, the weight average molecular weight of PGA used was about 5.1 ten thousand, the transesterification catalyst used was tetraisopropyl titanate, the heat stabilizer used was calcium palmitate soap, and the chain extender used was commercially available ADR 4385.
Example 4 the weight average molecular weight of the PLGA used was about 5.6 ten thousand, the mole percentage content of GA repeat units in the molecular chain was about 36%, the weight average molecular weight of the PGA used was about 5.1 ten thousand, the transesterification catalyst used was tetrabutyl titanate, the heat stabilizer used was a mixture of zinc palmitate soap and calcium linoleate soap in a mass ratio of 1: 1, and the chain extender used was commercially available ADR 4400;
the weight average molecular weight of PLGA used in example 5 was about 6.0 ten thousand, the mole percentage content of GA repeat units in the molecular chain was about 41%, the weight average molecular weight of PGA used was about 5.1 ten thousand, the transesterification catalyst used was tetrabutyl titanate, the heat stabilizer used was a mixture of zinc oleate soap and calcium palmitate soap in a mass ratio of 1: 2, and the chain extender used was a mixture of commercially available ADR4385 and ADR4400 in a mass ratio of 1: 4.
The functional control degradable master batch used in the above examples 1 to 5 is prepared by the following steps:
s1: mixing PLGA, PGA and an ester exchange catalyst according to the weight part, then melting and blending at 220-230 ℃, and then extruding and granulating to prepare premixed master batch;
s2: and melting and blending the premixed master batch, the chain extender and the heat stabilizer at the temperature of 180-200 ℃, and then extruding and granulating to obtain the functional adjustment degradable master batch.
Aiming at the preparation function, the process of adjusting the degradable master batch comprises the following steps:
the temperature used in step S1 of example 1 was about 220 ℃ and the temperature used in step S2 was about 180 ℃;
the temperature used in step S1 of example 2 was about 225 ℃ and the temperature used in step S2 was about 185 ℃;
the temperature used in step S1 of example 3 was about 225 ℃, and the temperature used in step S2 was about 190 ℃;
the temperature used in step S1 of example 4 was about 230 ℃ and the temperature used in step S2 was about 195 ℃;
the temperature used in step S1 of example 5 was about 230 ℃ and the temperature used in step S2 was about 200 ℃.
The above examples 1 to 5 were prepared by the following procedure:
step 1: adding the components into a double-screw extruder according to the parts by weight, heating, melting and blending, extruding by a die head of the double-screw extruder, attaching the extruded melt to the surface of a casting roller, and cooling to obtain a cast sheet;
step 2: carrying out biaxial stretching on the obtained cast sheet, and then carrying out heat setting to obtain a biaxial orientation film;
and step 3: and (3) performing electron beam irradiation on the prepared bidirectional oriented film, and then trimming and rolling.
In the process of preparing the heat shrinkable film, the specific process conditions adopted are as shown in the following table 3:
table 3 specific Process conditions
Note: in table 3, electron beam irradiation was performed in a nitrogen atmosphere.
Comparative examples 1-3 are provided below:
comparative example 1:
the comparative example does not contain the function-adjusting degradable master batch, and the rest is the same as the example 4.
Comparative example 2:
in the comparative example, PLGA was directly used in place of the function-adjusting degradable master batch, and the rest was the same as in example 4.
Comparative example 3:
in this comparative example, in the process of producing a heat shrinkable film, electron beam irradiation was not performed, and the rest was the same as in example 4.
And (3) performance testing:
the results of the performance test of the heat shrinkable films manufactured in the above examples 1 to 5 and comparative examples 1 to 3 are shown in the following table 4.
Table 4 results of performance testing
Note: in Table 4, the haze was measured in accordance with GB/T2410, the shrinkage was measured in accordance with BB/T0070-.
The thermal shrinkage films prepared in the above examples 1-5 pass the biodegradability test of GB/T19277-.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The biodegradable polyester heat shrinkable film is characterized in that: the composition is prepared from the following raw materials in parts by weight: 40-50 parts of PLA, 30-40 parts of PBAT, 15-30 parts of function-adjusting degradable master batch, 5-10 parts of compatilizer, 6-12 parts of plasticizer, 1-3 parts of slipping agent and 0.5-1 part of anti-aging agent.
2. The biodegradable polyester heat shrinkable film of claim 1, wherein: the function-adjusting degradable master batch is prepared from the following raw materials in parts by weight: 70-90 parts of PLGA, 10-30 parts of PGA, 0.5-2 parts of ester exchange catalyst, 0.1-0.6 part of heat stabilizer and 0.5-1.5 parts of chain extender.
3. The biodegradable polyester heat shrinkable film of claim 2, wherein: the weight average molecular weight of the PLGA is 3-6 ten thousand, and the mole percentage content of GA repeating units in a molecular chain is 10-40%.
4. The biodegradable polyester heat shrinkable film of claim 2, wherein: the ester exchange catalyst is one or two of tetrabutyl titanate or tetraisopropyl titanate, the heat stabilizer is one or more of calcium stearate soap, calcium oleate soap, calcium palmitoleate soap, calcium linoleate soap, zinc stearate soap, zinc palmitate soap or zinc oleate soap, and the chain extender is one or more of commercially available ADR4380, ADR4385 or ADR 4400.
5. The biodegradable polyester heat shrinkable film of claim 2, wherein: the preparation method of the function-adjusting degradable master batch comprises the following steps:
s1: mixing PLGA, PGA and an ester exchange catalyst according to the weight part, then melting and blending at 220-230 ℃, and then extruding and granulating to prepare premixed master batch;
s2: and melting and blending the premixed master batch, the chain extender and the heat stabilizer at the temperature of 180-200 ℃, and then extruding and granulating to obtain the functional adjustment degradable master batch.
6. The biodegradable polyester heat shrinkable film of claim 1, wherein the compatibilizer is glycidyl methacrylate grafted PLA, the melt index is 8-12g/10min (190 ℃,2.16kg), and the grafting ratio of glycidyl methacrylate is 0.61-1.02%.
7. The biodegradable polyester heat shrinkable film of claim 1, wherein: the plasticizer is prepared by mixing epoxidized soybean oil and pentaerythritol in a mass ratio of 2-4:1, the slipping agent is prepared by mixing erucamide and ethylene bis-stearamide in a mass ratio of 1-5:1, and the anti-aging agent is prepared by mixing 2- (2H-benzotriazole-2-yl) -4- (1,1,3, 3-tetramethyl butyl) phenol and barium terephthalate in a mass ratio of 1-3: 1.
8. Preparing the biodegradable polyester heat shrinkable film of claim 1, wherein: the method comprises the following steps:
step 1: adding the components into a double-screw extruder according to the parts by weight, heating, melting and blending, extruding by a die head of the double-screw extruder, attaching the extruded melt to the surface of a casting roller, and cooling to obtain a cast sheet;
step 2: carrying out biaxial stretching on the obtained cast sheet, and then carrying out heat setting to obtain a biaxial orientation film;
and step 3: and (3) performing electron beam irradiation on the prepared bidirectional oriented film, and then performing edge cutting and rolling to obtain the biodegradable polyester heat shrinkable film.
9. The method for preparing a biodegradable polyester heat shrinkable film according to claim 8, wherein: the temperature of the melt blending in the step 1 is 190-210 ℃, the temperature of a die head of a double-screw extruder is 210-220 ℃, the temperature of a casting roller is 30-60 ℃, the temperature of the biaxial stretching in the step 2 is longitudinal stretching and transverse stretching, the temperature of the biaxial stretching is controlled to be 70-90 ℃, the stretching speed is controlled to be 50-100mm/s, the stretching ratio is 3-5, and the temperature of the heat setting is 120-150 ℃.
10. The method for preparing a biodegradable polyester heat shrinkable film according to claim 8, wherein: the electron beam irradiation in the step 3 is carried out in an inert gas atmosphere, and the irradiation dose is 100-150 kGy.
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