CN107650360A - A kind of degradable poly methyl ethylene carbonate base microbedding coextruding composite material and preparation method thereof - Google Patents
A kind of degradable poly methyl ethylene carbonate base microbedding coextruding composite material and preparation method thereof Download PDFInfo
- Publication number
- CN107650360A CN107650360A CN201710889461.2A CN201710889461A CN107650360A CN 107650360 A CN107650360 A CN 107650360A CN 201710889461 A CN201710889461 A CN 201710889461A CN 107650360 A CN107650360 A CN 107650360A
- Authority
- CN
- China
- Prior art keywords
- ethylene carbonate
- degradable
- microbedding
- preparation
- composite material
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/49—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
The invention belongs to technical field of polymer processing, discloses a kind of degradable poly methyl ethylene carbonate base microbedding coextruding composite material and preparation method thereof.Preparation method of the present invention after lined polymethyl ethylene carbonate and the melting of degradable modifying agent through microbedding coextrusion by will be prepared.The present invention also provides the degradable poly methyl ethylene carbonate base microbedding coextruding composite material that above-mentioned preparation method obtains.The present invention uses two kinds of biodegradable polymers, one of which is lined polymethyl ethylene carbonate, another kind is biological degradation modification agent or PPC/ biodegradation modifier blends, it is fed respectively by two extruderses, after being alternately superimposed co-extruding machine head, the number of plies that superposition is prepared may be up to 128 layers of composite, and its mechanical property, barrier property are improved, and complete biodegradable, widen application of the pure lined polymethyl ethylene carbonate in packaging field.Preparation method technique of the present invention is simple, be easy to regulation and control, cost is cheap.
Description
Technical field
The invention belongs to technical field of polymer processing, more particularly to a kind of degradable poly methyl ethylene carbonate base microbedding
Coextruding composite material and preparation method thereof.
Background technology
Currently, as the environmental problem such as " greenhouse effects ", " white pollution " becomes increasingly conspicuous, degradable, reproducible high score
Sub- material gets growing concern for and paid attention to.Lined polymethyl ethylene carbonate (PPC) is by GHG carbon dioxide (CO2)
With the aliphatic polyester of expoxy propane synthesis, it can consume carbon dioxide in building-up process and can be one with complete biodegradable
The environmental protection macromolecule material of kind " two-way green ".PPC strand compliances are big, easy to process, possess good barrier property,
Instead of petroleum base barrier material ethylene-vinyl alcohol (EVOH), polyethylene (PE), polypropylene (PP), polyethylene terephthalate
The application of the conventional packaging materials such as ester (PET) above has broad prospects.But PPC is because its glass transition temperature is low, heat endurance
It is poor with mechanical property and it is extremely limited in actual applications.Using the method for blending and modifying to improving PPC's
Mechanical strength, heat endurance and barrier property have certain effect, but improved amplitude is little.Since in co-mixing system, each group
Point it is to exist usually in the form of dispersed phase or continuous phase, therefore more difficult ensures good dispersiveness and two-phase phase interaction
With this severely limits the further raising of co-mixing system combination property.
Research finds that can prepare the number of plies by microbedding coextrusion technology reaches hundreds of alternate multiple composite,
Layer structure is presented in the phase morphology of its each component all the time, and is alternately arranged under the overlay, and this give the unique power of microlayer composite
, barrier, optics, damping and electromagnetic performance.Currently, lined polymethyl ethylene carbonate is carried out using microbedding co-extrusion method both at home and abroad
Modified research report is few, therefore, is still needed come the technology of modified polymethyl ethylene carbonate using microbedding coextrusion method
Improve.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of degradable poly
Methyl ethylene carbonate base microbedding coextruding composite material.Composite materials property of the present invention, barrier property are improved, and complete
Complete biodegradable.
Another object of the present invention is to provide a kind of above-mentioned degradable poly methyl ethylene carbonate base microbedding coextru-lamination material
The preparation method of material.
The purpose of the present invention is realized by following proposal：
A kind of preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material, by by poly- methyl second
It is prepared after support carbonic ester (PPC) and the melting of degradable modifying agent through microbedding coextrusion.
The degradable modifying agent includes degradation plastic, including but not limited to polyvinyl alcohol (PVA), PLA (PLA),
Poly butylene succinate (PBS), polyadipate/butylene terephthalate (PBAT), polycaprolactone (PCL), starch and fibre
Tie up at least one of element.
When the degradable modifying agent includes polyvinyl alcohol (PVA), in addition to glycerine.
Described melting microbedding coextrusion especially by：
By multilayer times after lined polymethyl ethylene carbonate (PPC) and degradable modifying agent are extruded by two extruderses respectively
Increase device to be alternately superimposed, then sizing realization is carried out by mouth mold；
Or lined polymethyl ethylene carbonate (PPC), and lined polymethyl ethylene carbonate (PPC)/degradable modifying agent are mixed
Thing is alternately superimposed after being extruded respectively by two extruderses by multilayer multiplier, then carries out sizing realization by mouth mold.
Above-mentioned preparation method is specially that the superposition original paper of coextrusion machine is respectively enterd after the extruded machine of the component is extruded
In, superposition obtains 2n+1Layer, composite is obtained through sizing.
It is described when using lined polymethyl ethylene carbonate (PPC) and degradable modifying agent individually as two components
The mass ratio of lined polymethyl ethylene carbonate (PPC) and degradable modifying agent is 50:50~95:5.
When using lined polymethyl ethylene carbonate (PPC) as one of component, lined polymethyl ethylene carbonate (PPC)/can drop
When the modified agent composition of solution is as another component, lined polymethyl ethylene carbonate described in mixture (PPC) and degradable modification
The mass ratio of agent is 5:95~95:5.
When containing glycerine in system, the dosage of the glycerine is 1~5phr.
When using lined polymethyl ethylene carbonate (PPC) as one of component, lined polymethyl ethylene carbonate (PPC)/can drop
When the modified agent composition of solution is as another component, the mixture first carries out blending and modifying using screw extruder.
When the degradable modifying agent with PPC compatibilities are bad or processing temperature differs larger when (such as PVA), can be by adding
Adding solubilizer or plasticizer so as to improve both compatibilities and processing characteristics, preferably glycerine, its dosage is preferably 1~
5phr。
The present invention also provides the degradable poly methyl ethylene carbonate base microbedding coextru-lamination material that above-mentioned preparation method obtains
Material.
Microbedding co-extrusion technology can be by mechanical property, the preferable polymer of barrier property between pantostrat or high aspect ratio
The form of lamella of having a rest is present in other components, effectively extends the diffusion path of gas molecules in the polymer, so as to improve
The mechanical property and barrier property of composite.The present invention uses two kinds of biodegradable polymers, and one of which is poly-
Methyl ethylene carbonate (PPC), another kind is biological degradation modification agent or PPC/ biodegradation modifier blends, respectively by two
Platform extruder is fed, and after being alternately superimposed co-extruding machine head, the number of plies that superposition is prepared may be up to 128 layers of composite,
Its mechanical property, barrier property are improved, and complete biodegradable, have widened pure lined polymethyl ethylene carbonate in packaging field
Interior application.Preparation method technique of the present invention is simple, be easy to regulation and control, cost is cheap.
Brief description of the drawings
Fig. 1 is the microbedding co-extruder schematic diagram of embodiment 1.Wherein, A, B are extruder, and C is material feeding block, and D doubles for layer
Device, E are machine head port mould.
Fig. 2 is the SEM figures of 16 layers of PPC/PLA microbedding coextruding composite materials of embodiment 1.
Fig. 3 is the SEM figures of 32 layers of PPC/PLA microbedding coextruding composite materials of embodiment 2.
Fig. 4 is the SEM figures of 128 layers of PPC/PLA microbedding coextruding composite materials of embodiment 3.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
The material being related in the following example can obtain from commercial channel.
Wherein, PPC is purchased from Henan Tian Guan Group Co., Ltd, and number-average molecular weight is 10.71 × 104；
PLA is purchased from Nature Wroks companies of the U.S., trade mark 4032D；
PVA is purchased from Shanghai Ying Jia industry developments Co., Ltd, the trade mark 0588；
PPC, PLA, PVA can select the structure identical product of other manufacturer productions.
Embodiment 1：
700 grams of PPC are weighed, 300 grams of PLA, are added separately in two single screw extrusion machines, add PPC Screw Extrusion
Machine barrel zone temperature is 160~170 DEG C, and the screw extruder barrel temperature for adding PLA is 170~175 DEG C, layer multiplier and co-extrusion
The temperature setting of machine head port mould is 175 DEG C, and the rotating speed of two screw extruders is 20 revs/min.Using 2 sets of delaminating units
Layer multiplier, extrusion obtain 16 layers of PPC/PLA microbedding coextruding composite materials.The sheet microbedding coextru-lamination material obtained after extrusion
Material is immediately placed in vulcanizing press, and different sheet material and film are molded under 10MPa pressure, is prepared into standard batten.Root
Mechanical stretch performance test is carried out according to GB/T1040-2006；Moisture-vapor transmission test is carried out according to GB/T1037-1988；Root
OTR oxygen transmission rate test is carried out according to GB/T1038-2000.Record test result.Microbedding co-extruder schematic diagram is shown in Fig. 1.
Embodiment 2：
Coextrusion process process is substantially the same manner as Example 1, except that the quantity of delaminating units is different.The present embodiment
In, using the layer multiplier of 3 sets of delaminating units, extrusion obtains 32 layers of PPC/PLA microbedding coextruding composite materials.
Embodiment 3：
Coextrusion process process is substantially the same manner as Example 1, except that the quantity of delaminating units is different.The present embodiment
In, using the layer multiplier of 5 sets of delaminating units, extrusion obtains 128 layers of PPC/PLA microbedding coextruding composite materials.
(oxygen transmission coefficient, vapor are saturating for the tensile property data of product, barrier property data obtained by embodiment 1~3
Cross coefficient) it is as shown in table 1 below, and contrasted with pure PPC material.The PPC/PLA microbedding co-extrusions of 1~embodiment of embodiment 3 are answered
Condensation material is observed, and SEM figures are shown in Fig. 2~Fig. 4.
The performance parameter of the PPC/PLA microbedding coextruding composite materials of table 1
Embodiment 4：
450 grams of PPC are weighed, 50 grams of PVA, 15 grams of glycerine, are added in double screw extruder, double screw extruder highest
Heating Zone Temperature is 170 DEG C, and head temperature is 140 DEG C, and the rotating speed of screw extruder is 80 revs/min, pelletizing after extrusion, is obtained
PPC/PLA blend pellets.Itself and 500 grams of PPC are added separately in two single screw extrusion machines, the screw rod for adding PPC squeezes
Going out machine barrel zone temperature for 160~170 DEG C, the screw extruder barrel temperature for adding PPC/PLA blending materials is 170~175 DEG C,
The temperature setting of layer multiplier and co-extruding machine head mouth mold is 175 DEG C, and the rotating speed of two screw extruders is 20 revs/min.Adopt
With the layer multiplier of 3 sets of delaminating units, extrusion obtains 32 layers PPC/ (PPC/10PVA) microbedding coextruding composite material.After extrusion
Obtained sheet microbedding coextruding composite material is immediately placed in vulcanizing press, and different sheet materials is molded under 10MPa pressure
And film, it is prepared into standard batten.Mechanical stretch performance test is carried out according to GB/T1040-2006；According to GB/T1037-1988
Carry out moisture-vapor transmission test；OTR oxygen transmission rate test is carried out according to GB/T1038-2000.
Embodiment 5：
Coextrusion process process is substantially the same manner as Example 4, except that in PPC/PVA blends PVA quality percentage
Than difference.In the present embodiment, 400 grams of PPC and 100 gram of PVA are first weighed, 15 grams of glycerine obtain PPC/PVA blends, then with
500 grams of PPC carry out microbedding and are coextruded to obtain 32 layers PPC/ (PPC/20PVA) microbedding coextruding composite material.
Embodiment 6：
Coextrusion process process is substantially the same manner as Example 4, except that in PPC/PVA blends PVA quality percentage
Than difference.In the present embodiment, 350 grams of PPC and 150 gram of PVA are first weighed, 15 grams of glycerine obtain PPC/PVA blends, then with
500 grams of PPC carry out microbedding and are coextruded to obtain 32 layers PPC/ (PPC/30PVA) microbedding coextruding composite material.
(oxygen transmission coefficient, vapor are saturating for the tensile property data of product, barrier property data obtained by embodiment 4~6
Cross coefficient) it is as shown in table 2 below, and contrasted with pure PPC material.
The performance parameter of the PPC/PLA microbedding coextruding composite materials of table 2
Pass through above-mentioned experimental data：Microbedding coextruding composite material with the different numbers of plies is compared with pure PPC, composite wood
The tensile strength of material is substantially improved, and in the case where keeping good vapor transmission coefficient, oxygen transmission coefficient has obvious reduction, resistance
Separating performance is effectively improved, and present device is simple, and cost is cheap, significant effect, is easy to industrialized production, is advantageous to open up
Application of the wide pure lined polymethyl ethylene carbonate in packaging field.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
- A kind of 1. preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material, it is characterised in that pass through by It is prepared after lined polymethyl ethylene carbonate and the melting of degradable modifying agent through microbedding coextrusion.
- 2. the preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material according to claim 1, It is characterized in that：The degradable modifying agent includes polyvinyl alcohol, PLA, poly butylene succinate, polyadipate/to benzene At least one of dioctyl phthalate fourth diester, polycaprolactone, starch and cellulose.
- 3. the preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material according to claim 2, It is characterized in that：When the degradable modifying agent includes polyvinyl alcohol, in addition to glycerine.
- 4. the preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material according to claim 3, It is characterized in that：The dosage of the glycerine is 1~5phr.
- 5. the preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material according to claim 1, It is characterized in that：Described melting microbedding coextrusion especially by：Replace after lined polymethyl ethylene carbonate and degradable modifying agent are extruded by two extruderses respectively by multilayer multiplier Superposition, then sizing realization is carried out by mouth mold；Or lined polymethyl ethylene carbonate, and lined polymethyl ethylene carbonate/degradable modified agent composition are squeezed by two respectively Go out after machine extrusion and be alternately superimposed by multilayer multiplier, then sizing realization is carried out by mouth mold.
- 6. the preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material according to claim 5, It is characterized in that：Specially by the superposition original paper that coextrusion machine is respectively enterd after the extruded machine extrusion of the component, it is superimposed To 2n+1Layer, composite is obtained through sizing.
- 7. the preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material according to claim 5, It is characterized in that：It is described poly- when using lined polymethyl ethylene carbonate and degradable modifying agent individually as two components The mass ratio of methyl ethylene carbonate and degradable modifying agent is 50:50~95:5.
- 8. the preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material according to claim 5, It is characterized in that：When using lined polymethyl ethylene carbonate as one of component, lined polymethyl ethylene carbonate/degradable modifying agent When mixture is as another component, the mass ratio of lined polymethyl ethylene carbonate described in mixture and degradable modifying agent is 5: 95~95:5.
- 9. the preparation method of degradable poly methyl ethylene carbonate base microbedding coextruding composite material according to claim 5, It is characterized in that：When using lined polymethyl ethylene carbonate as one of component, lined polymethyl ethylene carbonate/degradable modifying agent When mixture is as another component, the mixture first carries out blending and modifying using screw extruder.
- A kind of 10. degradable poly methyl ethylene carbonate base microbedding coextruding composite material, it is characterised in that according to claim 1~ Preparation method described in 9 any one obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710889461.2A CN107650360A (en) | 2017-09-27 | 2017-09-27 | A kind of degradable poly methyl ethylene carbonate base microbedding coextruding composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710889461.2A CN107650360A (en) | 2017-09-27 | 2017-09-27 | A kind of degradable poly methyl ethylene carbonate base microbedding coextruding composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107650360A true CN107650360A (en) | 2018-02-02 |
Family
ID=61116148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710889461.2A Pending CN107650360A (en) | 2017-09-27 | 2017-09-27 | A kind of degradable poly methyl ethylene carbonate base microbedding coextruding composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107650360A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727752A (en) * | 2018-06-11 | 2018-11-02 | 中原工学院 | A method of preparing high strength poly vinyl alcohol composite hydrogel using in-situ fibrillation |
| CN112695260A (en) * | 2020-12-23 | 2021-04-23 | 潍坊学院 | Amorphous nanocrystalline iron-based composite soft magnetic alloy and preparation method thereof |
| CN112895659A (en) * | 2021-03-24 | 2021-06-04 | 华南理工大学 | Multilayer superposed composite material, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851406A (en) * | 2010-05-31 | 2010-10-06 | 河南天冠企业集团有限公司 | Completely degradable plastic film and production process thereof |
| CN102786788A (en) * | 2012-08-10 | 2012-11-21 | 中山大学 | Degradable poly-methyl ethylene carbonate base composite material and preparation method thereof |
| CN103087494A (en) * | 2013-01-25 | 2013-05-08 | 深圳市通产丽星股份有限公司 | Polymethyl ethylene carbonate modification method, modified material and application thereof |
| CN105017738A (en) * | 2014-11-26 | 2015-11-04 | 江苏天仁生物材料有限公司 | Fully biodegradable material taking polylactic acid/polymethyl ethylene carbonic ester as basic material and preparation method of fully biodegradable material |
-
2017
- 2017-09-27 CN CN201710889461.2A patent/CN107650360A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851406A (en) * | 2010-05-31 | 2010-10-06 | 河南天冠企业集团有限公司 | Completely degradable plastic film and production process thereof |
| CN102786788A (en) * | 2012-08-10 | 2012-11-21 | 中山大学 | Degradable poly-methyl ethylene carbonate base composite material and preparation method thereof |
| CN103087494A (en) * | 2013-01-25 | 2013-05-08 | 深圳市通产丽星股份有限公司 | Polymethyl ethylene carbonate modification method, modified material and application thereof |
| CN105017738A (en) * | 2014-11-26 | 2015-11-04 | 江苏天仁生物材料有限公司 | Fully biodegradable material taking polylactic acid/polymethyl ethylene carbonic ester as basic material and preparation method of fully biodegradable material |
Non-Patent Citations (1)
| Title |
|---|
| 徐景活: "共混改性和微层共挤制备聚甲基乙撑碳酸酯基复合材料及其结构与性能研究", 《共混改性和微层共挤制备聚甲基乙撑碳酸酯基复合材料及其结构与性能研究》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727752A (en) * | 2018-06-11 | 2018-11-02 | 中原工学院 | A method of preparing high strength poly vinyl alcohol composite hydrogel using in-situ fibrillation |
| CN108727752B (en) * | 2018-06-11 | 2021-02-05 | 中原工学院 | Method for preparing high-strength polyvinyl alcohol composite hydrogel by utilizing in-situ fiber forming |
| CN112695260A (en) * | 2020-12-23 | 2021-04-23 | 潍坊学院 | Amorphous nanocrystalline iron-based composite soft magnetic alloy and preparation method thereof |
| CN112895659A (en) * | 2021-03-24 | 2021-06-04 | 华南理工大学 | Multilayer superposed composite material, preparation method and application thereof |
| CN112895659B (en) * | 2021-03-24 | 2022-05-24 | 华南理工大学 | Multilayer superposed composite material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102501529B (en) | Biaxial drawing polylactic acid compound film with barrier property and preparation method thereof | |
| US8734710B2 (en) | Synergistic biopolymer blown film extrusion system and method | |
| CA2543306C (en) | Biodegradable multi-layer film | |
| CN103319865B (en) | Polylactic acid alloy film and application | |
| Cunha et al. | Film blowing of PHBV blends and PHBV‐based multilayers for the production of biodegradable packages | |
| CA2649164C (en) | Multilayer film and method for manufacturing same | |
| AU2009311593B2 (en) | Blends of polylactic acid and thermo-plastic polymers for packaging applications | |
| CN101797999B (en) | Packaging film for natural cellulose cigarette with heat sealing layer-coated surface and its preparation method | |
| CN102501511A (en) | Barrier heat sealing type biaxial tensile composite thin film and preparation method thereof | |
| US20220282037A1 (en) | High-barrier biodegradable Doypack and preparation method therefor | |
| CN110760169B (en) | Barrier material and preparation method thereof | |
| CN107650360A (en) | A kind of degradable poly methyl ethylene carbonate base microbedding coextruding composite material and preparation method thereof | |
| CN1531573A (en) | Ternary mixture of biodegradable polyesters and products obtained therefrom | |
| CN105722898B (en) | Biaxial stretch-formed product and ensiling film | |
| CN109229812A (en) | A kind of three-layer co-extruded complete biodegradable express packaging bag and preparation method thereof | |
| CN105017699A (en) | Biology-base degradable stretching film and preparing method thereof | |
| CN107304285A (en) | A kind of preparation method of polyester modification material and its membrane product | |
| AU2020203452A1 (en) | Biodegradable Sheets | |
| CN102350844A (en) | Polymer film and preparation method thereof | |
| CN107641307A (en) | A kind of lined polymethyl ethylene carbonate/polyvinyl alcohol degradable composite material and preparation method thereof | |
| CN107618245B (en) | Composite film and preparation method thereof | |
| CN103171219A (en) | Membrane consisting of inner-layer structure and outer-layer structure | |
| JP2013103438A (en) | Sheet and container using the same | |
| JP6452129B2 (en) | Multi-layer film structure containing renewable resource materials | |
| EP2451873A1 (en) | Biocling |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180202 |