CN103589124A - Fully-biodegradable PLA/PBAT composite film and making method thereof - Google Patents
Fully-biodegradable PLA/PBAT composite film and making method thereof Download PDFInfo
- Publication number
- CN103589124A CN103589124A CN201210289135.5A CN201210289135A CN103589124A CN 103589124 A CN103589124 A CN 103589124A CN 201210289135 A CN201210289135 A CN 201210289135A CN 103589124 A CN103589124 A CN 103589124A
- Authority
- CN
- China
- Prior art keywords
- poly
- butyleneglycol
- district
- ester
- acid
- 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.)
- Granted
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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/397—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using a single screw
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention belongs to the technical field of high-molecular materials, and relates to a PLA/PBAT composite film and a making method thereof. The composite film is made by using the following components, by weight, 10-90 parts of polylactic acid, 10-90 parts of PBAT, 0.04-2.5 parts of a compatibilizer A, 0.04-2.5 parts of a compatibilizer B, 0-3 parts of a lubricant, 0-3 parts of an antioxidant and 1-50 parts of a filler. A blend provided by the invention has a very good flexibility, and the made film can be fully biodegraded, and can be widely used in the field of films.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of PLA/PBAT laminated film and preparation method thereof.
Background technology
The use of plastics film has been penetrated into the every field of people's life, is widely used as food product pack, electric equipment products packing and market shopping bag, refuse bag etc.Traditional plastic film material, if the starting material of polypropylene (PP) film, polyethylene (PE) film etc. are oil, uses and is discarded into hard degradation in nature, to environment, has caused huge harm.Be accompanied by the day by day exhausted and continuous enhancing of people to environmental consciousness of petroleum resources, the environmentally friendly macromolecular material of exploitation degradable is applied to thin-film material field to become following Developing mainstream.
Poly(lactic acid) (PLA) is that the starch being extracted by renewable plant resourceses such as corn, potatos is converted into glucose, and glucose becomes lactic acid by fermentation, the aliphatic polyester being further polymerized.The glass transition temperature Tg of PLA is approximately 55 ℃, and about 180 ℃ of fusing point Tm, has good biocompatibility and high strength, and can complete biodegradable, and the final product after degraded is water and carbonic acid gas, thereby, nontoxic, can not cause environmental pollution.Although the high comprehensive performance of PLA, intensity is higher, its poor toughness, general 4% left and right of elongation at break of pure PLA.
Poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester (PBAT) is a kind of aliphatic-aromatic copolyester.This copolyesters has good biodegradability, and the final product of degraded is water and carbonic acid gas, is a kind of environmentally friendly macromolecular material, and it also has good ductility and toughness simultaneously, has again good thermotolerance and impact property.
Therefore, by PLA and PBAT blend, utilize both performance advantages complementary, regulate both blend ratios, not only can obtain the blend that intensity is higher, but also can improve the snappiness of blend, and utilize film prepared by this blend can realize complete biodegradable, be a kind of environmental friendliness shaped material.
According to prior art is retrieved and found, Chinese patent CN102516729 discloses a kind of completely biological degradation polylactic acid composition and method of making the same, in PLA and PBAT co-mixing system, added bisoxazoline class chainextender improve co-mixing system in the interface compatibility of two components; Documents and materials have also reported respectively that employing polyoxyethylene glycol (PEG), polycaprolactone (PCL) and commodity are called Lotader AX8900, Joncryl ADR-4368, ADR-4370 epoxies chainextender improves the consistency of PLA and PBAT blend components, thereby prepares high performance full-biodegradable film simultaneously.But the main p-COOH of bisoxazoline class chainextender shows as higher activity, and epoxies chainextender need to just can have higher reactive behavior at higher temperature, but excess Temperature can make polyester components, degraded is serious.
Summary of the invention
The object of the invention is to provide a kind of PLA/PBAT laminated film and preparation method thereof for overcoming the defect of prior art.
Adopt technical solution of the present invention not only can improve well the consistency of blend two components, and resulting blend can be for the preparation of full-biodegradable film, this film can be widely used in market shopping bag, refuse bag, food pack, agricultural with fields such as films.
For achieving the above object, the present invention is by the following technical solutions:
A laminated film, by the component that comprises following weight part, made:
Poly(lactic acid) 10-90 part,
Poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester 10-90 part,
Expanding material A 0.04-2.5 part,
Expanding material B 0.04-2.5 part,
Lubricant 0-3 part,
Oxidation inhibitor 0-3 part,
Filler 1-50 part.
Described poly(lactic acid) is mainly to be obtained by Pfansteihl polymerization, also contains a small amount of D-ALPHA-Hydroxypropionic acid in system simultaneously, and preferable weight-average molecular weight is 40000-200000.
Described poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester (PBAT) is with terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT), 1,4-butyleneglycol (BG) and hexanodioic acid (AA) are for polymerizable raw material obtains, and preferable weight-average molecular weight is 20000-130000.
Described expanding material A is selected from bisoxazoline class chainextender, further preferred one or more in 2,2 '-bis-(2-oxazolines) or 1,3-penylene-bis-(2-oxazolines).
Described expanding material B is selected from the isocyanates chainextender of functionality >=2, one or more in further preferred hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, an xylylene diisocyanate, PPDI, dimethyl diphenyl vulcabond, isophorone diisocyanate, lysinediisocyanate or polymethylene multi-phenenyl isocyanate.
Described lubricant is one or more in Zinic stearas, calcium stearate, sodium stearate, Magnesium Stearate, barium stearate, amine hydroxybenzene, erucicamide, alkylidene group two fatty amides, ethylene bis stearamide, paraffin or polyethylene wax etc.
Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] one or more in pentaerythritol ester (antioxidant 1010), β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol acid esters (antioxidant 1076), 2-methylene-bis (4-methyl-6-tert-butylphenol) (antioxidant 2246), three (2.4-di-tert-butyl-phenyl) phosphorous acid ester (irgasfos 168).
Described filler is one or more in calcium carbonate, kaolin, silicon-dioxide, mica, polynite, clay, barium carbonate, sodium carbonate, talcum powder, aluminum oxide, barium sulfate, sal epsom etc.
A preparation method for above-mentioned PLA/PBAT laminated film, comprises the steps:
(1) poly(lactic acid), poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester and paddle dryer are processed;
(2) by said ratio, take each component raw material, poly(lactic acid), poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester, expanding material A, expanding material B, lubricant, oxidation inhibitor and filler are mixed;
(3) material mixing is joined to melt blending in twin screw extruder, extruding pelletization;
(4) by the pellet drying treatment obtaining through twin-screw extrusion; (5) dried pellet in step (4) is joined in single screw extrusion machine, extrusion-blown modling, obtains full-biodegradable film.
In described step (1), the drying temperature of poly(lactic acid), poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester is 60-80 ℃, and be 6-24h time of drying; The drying temperature of filler is 100-120 ℃, and the time is 5-10h; Drying plant is vacuum drying oven or convection oven.
In described step (3), twin screw extruder extrusion temperature is 110-180 ℃, screw speed 60-600rpm, and screw slenderness ratio L/D is 40-50:1.
In described step (4), drying temperature is 60-80 ℃, and be 6-24h time of drying, and drying plant is vacuum drying oven or convection oven.
In described step (5), single screw extrusion machine extrusion temperature is 130-170 ℃, screw speed 100-400rpm, and screw slenderness ratio L/D is 20-40:1; The die head bore of single screw extrusion machine is 3-5:1 with bubble pipe diameter ratio.
The present invention has following beneficial effect:
Blend preparation technology provided by the present invention is simple, and between polymeric matrix, interface compatibility is good; Blend not only has good mechanical property, but also has good snappiness, and the film biodegradable of preparation can be widely used in various films field.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Experimental raw in embodiment:
PLA: poly(lactic acid), Natureworks company provides, and the trade mark is respectively 4032D, 2002D; The PLA polymer raw main component of this trade mark is Pfansteihl, also contains the D-ALPHA-Hydroxypropionic acid of <5% simultaneously, and weight-average molecular weight Mw scope is 10-20 ten thousand.
PBAT: poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester, what embodiment 1-6 was used is that BASF Aktiengesellschaft produces, and the trade mark is the PBAT of Ecoflex FBX7011, and weight-average molecular weight Mw is 12.4 ten thousand.
The PBAT weight-average molecular weight of using in embodiment 7 is 2.5 ten thousand.
Mechanics Performance Testing: tensile property testing standard is ASTM D638, draw speed 50mm/min.
Embodiment 1
(1) by PLA(4032D) and PBAT drying treatment 12h in 80 ℃ of convection oven, calcium carbonate is drying treatment 6h in 105 ℃ of convection oven;
(2) then get 90 parts of PLA, 10 parts of PBAT, 0.04 part 2,2 '-bis-(2-oxazolines), 2.4 parts of hexamethylene diisocyanates, 0.6 part of calcium stearate, 0.1 part of antioxidant 1010,10 parts of calcium carbonate normal temperature mixing 5min in high mixer;
(3) mixture obtaining is joined to extruding pelletization in dual-screw-stem machine, each district's temperature of dual-screw-stem machine is: 150 160 160 170 170 175 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 180 ℃ of heads; Screw speed is 200rpm, length-to-diameter ratio L/D=40/1;
(4) pellet step (3) being obtained is drying treatment 12h in 80 ℃ of convection oven;
(5) dried pellet in step (4) is joined to extrusion-blown modling in single-screw machine, each district's temperature of single-screw machine is: 120 140 160 170 170 170 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 165 ℃ of heads; Screw speed is 150rpm, length-to-diameter ratio L/D=25/1, and the die head bore of single screw extrusion machine is 3:1 with bubble pipe diameter ratio.
Embodiment 2
(1) the drying treatment 12h in 80 ℃ of baking ovens by PLA (4032D) and PBAT, talcum powder is drying treatment 6h in 110 ℃ of baking ovens;
(2) then get 60 parts of PLA, 40 parts of PBAT, 0.9 part 1,3-penylene-bis-(2-oxazoline), 0.04 part of diphenylmethanediisocyanate, 0.3 part of amine hydroxybenzene, 0.1 part of antioxidant 1076,20 parts of talcum powder normal temperature mixing 5min in high mixer;
(3) mixture obtaining is joined to extruding pelletization in dual-screw-stem machine, each district's temperature of dual-screw-stem machine is: 150 160 160 170 170 175 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 180 ℃ of heads; Screw speed is 200rpm, length-to-diameter ratio L/D=40/1;
(4) pellet step (3) being obtained is drying treatment 12h in 80 ℃ of convection oven;
(5) dried pellet in step (4) is joined to extrusion-blown modling in single-screw machine, each district's temperature of single-screw machine is: 120 140 160 170 170 170 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 165 ℃ of heads; Screw speed is 150rpm, length-to-diameter ratio L/D=25/1, and the die head bore of single screw extrusion machine is 4:1 with bubble pipe diameter ratio.
Embodiment 3
(1) the drying treatment 12h in 80 ℃ of baking ovens by PLA (2002D) and PBAT, polynite is drying treatment 6h in 105 ℃ of baking ovens;
(2) then get 10 parts of PLA, 90 parts of PBAT, 2.4 part 2,2 '-bis-(2-oxazolines), 0.6 part of polymethylene multi-phenenyl isocyanate, 0.1 part of erucicamide, 0.1 part of irgasfos 168,50 parts of polynite normal temperature mixing 5min in high mixer;
(3) mixture obtaining is joined to extruding pelletization in dual-screw-stem machine, each district's temperature of dual-screw-stem machine is: 150 160 160 170 170 175 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 180 ℃ of heads; Screw speed is 200rpm, length-to-diameter ratio L/D=40/1;
(4) pellet step (3) being obtained is drying treatment 12h in 80 ℃ of convection oven;
(5) dried pellet in step (4) is joined to extrusion-blown modling in single-screw machine, each district's temperature of single-screw machine is: 120 140 160 170 170 170 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 165 ℃ of heads; Screw speed is 150rpm, length-to-diameter ratio L/D=25/1, and the die head bore of single screw extrusion machine is 5:1 with bubble pipe diameter ratio.
Embodiment 4
(1) the drying treatment 12h in 80 ℃ of baking ovens by PLA (2002D) and PBAT, silicon-dioxide is drying treatment 6h in 105 ℃ of baking ovens;
(2) then get 70 parts of PLA, 30 parts of PBAT, 1.1 part 1,3-penylene-bis-(2-oxazoline), 0.9 part of lysinediisocyanate, 0.2 part of ethylene bis stearamide, 0.1 part of antioxidant 1010,30 parts of calcium carbonate normal temperature mixing 5min in high mixer;
(3) mixture obtaining is joined to extruding pelletization in dual-screw-stem machine, each district's temperature of dual-screw-stem machine is: 150 160 160 170 170 175 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 180 ℃ of heads; Screw speed is 200rpm, length-to-diameter ratio L/D=40/1;
(4) pellet step (3) being obtained is drying treatment 12h in 80 ℃ of convection oven;
(5) dried pellet in step (4) is joined to extrusion-blown modling in single-screw machine, each district's temperature of single-screw machine is: 120 140 160 170 170 170 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 165 ℃ of heads; Screw speed is 150rpm, length-to-diameter ratio L/D=25/1, and the die head bore of single screw extrusion machine is 5:1 with bubble pipe diameter ratio.
The performance test of the full-biodegradable film that embodiment 1-4 makes is as following table 1:
Table 1
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength/MPa | 61 | 48 | 37 | 54 |
| Elongation at break/% | 185 | 273 | 316 | 217 |
As can be seen from Table 1, the blend after modification not only has higher tensile strength, and elongation at break is also larger simultaneously, and the material after modification can be directly used in wrapping material such as preparing film.
Embodiment 5
(1) the drying treatment 12h in 80 ℃ of baking ovens by PLA (4032D) and PBAT, silicon-dioxide is drying treatment 6h in 105 ℃ of baking ovens;
(2) then get 30 parts of PLA, 70 parts of PBAT, 2 part 1,3-penylene-bis-(2-oxazoline), 2 parts of tolylene diisocyanates, 3 parts of paraffin, 3 parts of antioxidant 2246s, 30 parts of silicon-dioxide normal temperature mixing 5min in high mixer;
(3) mixture obtaining is joined to extruding pelletization in dual-screw-stem machine, each district's temperature of dual-screw-stem machine is: 150 160 160 170 170 175 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 180 ℃ of heads; Screw speed is 200rpm, length-to-diameter ratio L/D=50/1;
(4) pellet step (3) being obtained is drying treatment 12h in 80 ℃ of convection oven;
(5) dried pellet in step (4) is joined to extrusion-blown modling in single-screw machine, each district's temperature of single-screw machine is: 120 140 160 170 170 170 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 165 ℃ of heads; Screw speed is 150rpm, length-to-diameter ratio L/D=20/1, and the die head bore of single screw extrusion machine is 3:1 with bubble pipe diameter ratio.
Embodiment 6
(1) the drying treatment 12h in 80 ℃ of baking ovens by PLA (4032D) and PBAT, sal epsom is drying treatment 6h in 105 ℃ of baking ovens;
(2) then get 40 parts of PLA, 60 parts of PBAT, 2.5 part 2,2 '-bis-(2-oxazolines), 2.5 parts of isophorone diisocyanates, 40 parts of sal epsom normal temperature mixing 5min in high mixer;
(3) mixture obtaining is joined to extruding pelletization in dual-screw-stem machine, each district's temperature of dual-screw-stem machine is: 150 160 160 170 170 175 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 180 ℃ of heads; Screw speed is 200rpm, length-to-diameter ratio L/D=45/1;
(4) pellet step (3) being obtained is drying treatment 12h in 80 ℃ of convection oven;
(5) dried pellet in step (4) is joined to extrusion-blown modling in single-screw machine, each district's temperature of single-screw machine is: 120 140 160 170 170 170 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 165 ℃ of heads; Screw speed is 150rpm, length-to-diameter ratio L/D=40/1, and the die head bore of single screw extrusion machine is 4:1 with bubble pipe diameter ratio.
Embodiment 7
(1) the drying treatment 12h in 80 ℃ of baking ovens by PLA (4032D) and PBAT, sal epsom is drying treatment 6h in 105 ℃ of baking ovens;
(2) then get 40 parts of PLA, 60 parts of PBAT, 2.5 part 2,2 '-bis-(2-oxazolines), 2.5 parts of isophorone diisocyanates, 40 parts of sal epsom normal temperature mixing 5min in high mixer;
(3) mixture obtaining is joined to extruding pelletization in dual-screw-stem machine, each district's temperature of dual-screw-stem machine is: 150 160 160 170 170 175 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 180 ℃ of heads; Screw speed is 200rpm, length-to-diameter ratio L/D=45/1;
(4) pellet step (3) being obtained is drying treatment 12h in 80 ℃ of convection oven;
(5) dried pellet in step (4) is joined to extrusion-blown modling in single-screw machine, each district's temperature of single-screw machine is: 120 140 160 170 170 170 ℃, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district, 165 ℃ of heads; Screw speed is 150rpm, length-to-diameter ratio L/D=40/1, and the die head bore of single screw extrusion machine is 4:1 with bubble pipe diameter ratio.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. poly(lactic acid)/poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester laminated film, is characterized in that: by the component that comprises following weight part, made:
Poly(lactic acid) 10-90 part,
Poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester 10-90 part,
Expanding material A 0.04-2.5 part,
Expanding material B 0.04-2.5 part,
Lubricant 0-3 part,
Oxidation inhibitor 0-3 part,
Filler 1-50 part.
2. poly(lactic acid) according to claim 1/poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester laminated film, is characterized in that: the weight-average molecular weight of described poly(lactic acid) is 40000-200000;
Or the weight-average molecular weight of described poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester is 20000-130000.
3. poly(lactic acid) according to claim 1/poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester laminated film, it is characterized in that: described expanding material A is selected from bisoxazoline class chainextender, further preferably 2, one or more in 2 '-bis-(2-oxazolines) or 1,3-penylene-bis-(2-oxazolines);
Or described expanding material B is selected from the isocyanates chainextender of functionality >=2, one or more in further preferred hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, an xylylene diisocyanate, PPDI, dimethyl diphenyl vulcabond, isophorone diisocyanate, lysinediisocyanate or polymethylene multi-phenenyl isocyanate.
4. poly(lactic acid) according to claim 1/poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester laminated film, is characterized in that: described lubricant is one or more in Zinic stearas, calcium stearate, sodium stearate, Magnesium Stearate, barium stearate, amine hydroxybenzene, erucicamide, alkylidene group two fatty amides, ethylene bis stearamide, paraffin or polyethylene wax.
5. poly(lactic acid) according to claim 1/poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester laminated film, it is characterized in that: described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] one or more in pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol acid esters, 2-methylene-bis (4-methyl-6-tert-butylphenol) or three (2.4-di-tert-butyl-phenyl) phosphorous acid ester.
6. poly(lactic acid) according to claim 1/poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester laminated film, is characterized in that: described filler is one or more in calcium carbonate, kaolin, silicon-dioxide, mica, polynite, clay, barium carbonate, sodium carbonate, talcum powder, aluminum oxide, barium sulfate or sal epsom.
7. the preparation method of arbitrary described poly(lactic acid)/poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester laminated film in the claims 1-6, is characterized in that: comprise the steps:
(1) poly(lactic acid), poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester and paddle dryer are processed;
(2) by proportioning claimed in claim 1, take each component raw material, poly(lactic acid), poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester, expanding material A, expanding material B, lubricant, oxidation inhibitor and filler are mixed;
(3) material mixing is joined to melt blending in twin screw extruder, extruding pelletization;
(4) by the pellet drying treatment obtaining through twin-screw extrusion;
(5) dried pellet in step (4) is joined in single screw extrusion machine, extrusion-blown modling, obtains full-biodegradable film.
8. preparation method according to claim 7, is characterized in that: in described step (1), the drying temperature of poly(lactic acid), poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester is 60-80 ℃, and be 6-24h time of drying; The drying temperature of filler is 100-120 ℃, and the time is 5-10h; Drying plant is vacuum drying oven or convection oven.
9. preparation method according to claim 7, is characterized in that: in described step (3), twin screw extruder extrusion temperature is 110-180 ℃, screw speed 60-600rpm, and screw slenderness ratio L/D is 40-50:1;
Or drying temperature is 60-80 ℃ in described step (4), be 6-24h time of drying, and drying plant is vacuum drying oven or convection oven.
10. preparation method according to claim 7, is characterized in that: in described step (5), single screw extrusion machine extrusion temperature is 130-170 ℃, screw speed 100-400rpm, and screw slenderness ratio L/D is 20-40:1; The die head bore of single screw extrusion machine is 3-5:1 with bubble pipe diameter ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210289135.5A CN103589124B (en) | 2012-08-14 | 2012-08-14 | A kind of complete biodegradable PLA/PBAT laminated film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210289135.5A CN103589124B (en) | 2012-08-14 | 2012-08-14 | A kind of complete biodegradable PLA/PBAT laminated film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103589124A true CN103589124A (en) | 2014-02-19 |
| CN103589124B CN103589124B (en) | 2016-12-07 |
Family
ID=50079458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210289135.5A Active CN103589124B (en) | 2012-08-14 | 2012-08-14 | A kind of complete biodegradable PLA/PBAT laminated film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103589124B (en) |
Cited By (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937194A (en) * | 2014-05-12 | 2014-07-23 | 东莞市信诺橡塑工业有限公司 | PC (Poly Carbonate)/PA (Polyamide) 66 composition and preparation method thereof |
| CN103937192A (en) * | 2014-05-12 | 2014-07-23 | 东莞市信诺橡塑工业有限公司 | PC/PA 11 (polycarbonate/polyamide 11) composition and preparation method thereof |
| CN105368013A (en) * | 2015-11-11 | 2016-03-02 | 吉林省开顺新材料有限公司 | Method for improving PLA and PBAT compatibility |
| CN105860462A (en) * | 2015-01-23 | 2016-08-17 | 深圳王子新材料股份有限公司 | Polylactic acid based composite material and preparation method and application thereof |
| CN106009564A (en) * | 2016-06-22 | 2016-10-12 | 新疆加福萨斯石油设备有限公司 | Degradable and environment-friendly anti-seepage film for oil field and preparation method of degradable environment-friendly anti-seepage film |
| CN106519618A (en) * | 2016-11-23 | 2017-03-22 | 吉林中粮生化有限公司 | High-polylactic acid-content film and preparation method thereof |
| CN106566210A (en) * | 2016-10-26 | 2017-04-19 | 深圳王子新材料股份有限公司 | Biodegradable bubble film and preparation method thereof |
| CN106674923A (en) * | 2016-12-13 | 2017-05-17 | 常州绿之源高分子材料有限公司 | Controllable-degradation PBAT/PLA (poly(butyleneadipate-co-terephthalate)/polylactic acid) composite film and preparation method thereof |
| CN106750253A (en) * | 2016-12-13 | 2017-05-31 | 常州绿之源高分子材料有限公司 | A kind of PBAT/PLA blendings bulking agent and preparation method thereof |
| CN106751568A (en) * | 2016-12-13 | 2017-05-31 | 常州绿之源高分子材料有限公司 | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof |
| CN106916421A (en) * | 2017-04-07 | 2017-07-04 | 常州大学 | One kind enhancing is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）Ester degradable material |
| CN107118309A (en) * | 2017-06-26 | 2017-09-01 | 浙江海轩科技有限公司 | A kind of biodegradable polyesters alloy and preparation method thereof |
| CN107522987A (en) * | 2017-09-29 | 2017-12-29 | 安徽同利塑胶彩印有限公司 | A kind of food pack and preparation method thereof |
| CN107955350A (en) * | 2017-12-03 | 2018-04-24 | 山东天野生物降解新材料科技有限公司 | A kind of complete biodegradable drug resistance ground film composition and preparation method thereof |
| CN108003575A (en) * | 2017-12-21 | 2018-05-08 | 苏州星火丰盈环保包装有限公司 | A kind of PLA, PBAT and PCL blend refuse bag and preparation method thereof |
| CN108003583A (en) * | 2017-12-21 | 2018-05-08 | 苏州星火丰盈环保包装有限公司 | A kind of high tensile complete biodegradable refuse bag production technology |
| CN108102307A (en) * | 2017-12-21 | 2018-06-01 | 苏州星火丰盈环保包装有限公司 | A kind of high elongation at tear complete biodegradable refuse bag production technology |
| CN108102308A (en) * | 2017-12-21 | 2018-06-01 | 苏州星火丰盈环保包装有限公司 | A kind of high-compatibility complete biodegradable refuse bag and preparation method thereof |
| CN108102323A (en) * | 2017-12-21 | 2018-06-01 | 苏州星火丰盈环保包装有限公司 | A kind of complete biodegradable refuse bag and preparation method thereof |
| CN108219406A (en) * | 2017-11-29 | 2018-06-29 | 中国科学院宁波材料技术与工程研究所 | A kind of flame retardant type Based Full-degradable Plastics Film and preparation method thereof |
| CN108359223A (en) * | 2017-12-27 | 2018-08-03 | 杨红梅 | A kind of biodegradable polymer blend and its application |
| CN108912630A (en) * | 2018-06-08 | 2018-11-30 | 黑龙江鑫达企业集团有限公司 | A kind of easily peelable environment-friendlythin thin film and its technique for adsorbing bamboo chopsticks |
| WO2019010767A1 (en) * | 2017-07-11 | 2019-01-17 | 河南谷润聚合物有限公司 | Method for synthesizing pbat-pla copolyester by means of copolymerization |
| CN109679074A (en) * | 2018-11-30 | 2019-04-26 | 中粮集团有限公司 | A kind of polylactic acid poly shares compound stabilizer and application thereof and application method |
| CN109762307A (en) * | 2018-12-20 | 2019-05-17 | 上海昶法新材料有限公司 | A kind of dedicated antibacterial matrices of biodegradable garbage bag and preparation method thereof |
| CN109825048A (en) * | 2019-02-20 | 2019-05-31 | 华南理工大学 | A kind of PLA/PBAT composite material and preparation method |
| CN110283438A (en) * | 2019-07-22 | 2019-09-27 | 中国科学院长春应用化学研究所 | A kind of base resin and blow molding degradable films of blow molding degradable films |
| CN110499009A (en) * | 2019-08-26 | 2019-11-26 | 青岛嘉泽包装有限公司 | A kind of application of degradable bracing wire basement membrane and preparation method in dismounting bracing wire |
| CN110845830A (en) * | 2019-11-13 | 2020-02-28 | 青岛润兴塑料新材料有限公司 | Starch filled PLA/PBAT full-biodegradable composite material and preparation method thereof |
| CN110894344A (en) * | 2018-09-12 | 2020-03-20 | 上海昶法新材料有限公司 | Papermaking waste modified antibacterial degradable garbage bag and preparation method thereof |
| CN111073232A (en) * | 2019-12-30 | 2020-04-28 | 武汉华丽环保科技有限公司 | Reinforced filling type full-biodegradable plastic film and preparation method thereof |
| CN111976244A (en) * | 2020-08-31 | 2020-11-24 | 无锡纯宇环保制品有限公司 | Full-biodegradable bubble film composite material and preparation method thereof |
| CN112210195A (en) * | 2020-10-10 | 2021-01-12 | 莱涤新材料(宁波)有限公司 | Biodegradable polylactic acid plastic bag and preparation method thereof |
| CN112341763A (en) * | 2020-09-11 | 2021-02-09 | 喀什中天节水科技有限公司 | PBAT composite material film and preparation method and application thereof |
| CN112662147A (en) * | 2020-12-23 | 2021-04-16 | 青岛润兴塑料新材料有限公司 | High-performance ternary compound biodegradable film |
| CN112679928A (en) * | 2020-12-28 | 2021-04-20 | 东莞市三至新材料技术有限公司 | Full-biodegradable antibacterial PLA/PBAT film and preparation method thereof |
| CN112826299A (en) * | 2021-03-09 | 2021-05-25 | 无锡方成包装科技股份有限公司 | Biodegradable coated paper straw with reinforcing ribs and preparation method thereof |
| CN113045836A (en) * | 2019-12-28 | 2021-06-29 | 合肥杰事杰新材料股份有限公司 | Degradable high impact polystyrene resin and preparation method thereof |
| CN113429759A (en) * | 2021-07-13 | 2021-09-24 | 山东瑞丰高分子材料股份有限公司 | PBAT composite modified biodegradable material and preparation method thereof |
| CN113480838A (en) * | 2021-07-30 | 2021-10-08 | 宜兴西工维新科技有限公司 | PLA/PBAT film capable of being rapidly degraded and preparation method thereof |
| CN113831708A (en) * | 2021-09-13 | 2021-12-24 | 江西省萍乡市轩品塑胶制品有限公司 | Full-biodegradable film containing coal gangue and preparation method thereof |
| CN114230987A (en) * | 2022-01-11 | 2022-03-25 | 南通富士美帽业有限公司 | Environment-friendly high-transparency composite material capable of being sewn and preparation method thereof |
| CN114369346A (en) * | 2021-11-30 | 2022-04-19 | 苏州星火丰盈环保包装有限公司 | Biodegradable plastic garbage bag and preparation method thereof |
| CN114524958A (en) * | 2022-03-16 | 2022-05-24 | 万华化学集团股份有限公司 | Preparation method of degradable barrier film |
| WO2022177514A1 (en) * | 2020-12-31 | 2022-08-25 | Gema Elektro Plastik Ve Elektronik San. Dis Tic. A. S. | A polymer composition having inorganic additive and production method thereof |
| CN115160740A (en) * | 2022-06-10 | 2022-10-11 | 上海昶法新材料有限公司 | Bio-based fully-degradable controllable agricultural film and preparation method thereof |
| CN115466491A (en) * | 2022-10-09 | 2022-12-13 | 合肥工业大学 | High-modulus degradable PBAT/PLA compound and preparation method thereof |
| CN115558139A (en) * | 2022-10-11 | 2023-01-03 | 福建凯基高分子材料股份有限公司 | Preparation process of antibacterial puncture-resistant PBAT composite film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504506A (en) * | 2011-11-09 | 2012-06-20 | 上海交通大学 | Method for compatibilizing PLA/PBAT alloy |
| CN102516729A (en) * | 2011-12-08 | 2012-06-27 | 江南大学 | Completely biodegradable polylactic acid composition and its preparation method |
-
2012
- 2012-08-14 CN CN201210289135.5A patent/CN103589124B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504506A (en) * | 2011-11-09 | 2012-06-20 | 上海交通大学 | Method for compatibilizing PLA/PBAT alloy |
| CN102516729A (en) * | 2011-12-08 | 2012-06-27 | 江南大学 | Completely biodegradable polylactic acid composition and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| J.KYLMA ET AL.: "Chain extending of lactic acid oligomers. Effect of 2,2’-bis(2-oxazoline) on 1,6-hexamethylene diisocyanate linking reacting", 《POLYMER》 * |
| JUKKA TUOMINEN ET AL.: "Chain extending of lactic acid oligomers. 2. Increase of molecular weight with 1,6-hexamethylene diisocyanate and 2,2’-bis(2-oxazoline)", 《POLYMER》 * |
Cited By (59)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937194A (en) * | 2014-05-12 | 2014-07-23 | 东莞市信诺橡塑工业有限公司 | PC (Poly Carbonate)/PA (Polyamide) 66 composition and preparation method thereof |
| CN103937192A (en) * | 2014-05-12 | 2014-07-23 | 东莞市信诺橡塑工业有限公司 | PC/PA 11 (polycarbonate/polyamide 11) composition and preparation method thereof |
| CN103937192B (en) * | 2014-05-12 | 2015-10-28 | 东莞市信诺橡塑工业有限公司 | PC/PA11 composition and method of making the same |
| CN105860462A (en) * | 2015-01-23 | 2016-08-17 | 深圳王子新材料股份有限公司 | Polylactic acid based composite material and preparation method and application thereof |
| CN105368013A (en) * | 2015-11-11 | 2016-03-02 | 吉林省开顺新材料有限公司 | Method for improving PLA and PBAT compatibility |
| CN106009564A (en) * | 2016-06-22 | 2016-10-12 | 新疆加福萨斯石油设备有限公司 | Degradable and environment-friendly anti-seepage film for oil field and preparation method of degradable environment-friendly anti-seepage film |
| CN106566210A (en) * | 2016-10-26 | 2017-04-19 | 深圳王子新材料股份有限公司 | Biodegradable bubble film and preparation method thereof |
| CN106566210B (en) * | 2016-10-26 | 2018-12-04 | 深圳王子新材料股份有限公司 | Biodegradable bubble chamber film and preparation method thereof |
| CN106519618A (en) * | 2016-11-23 | 2017-03-22 | 吉林中粮生化有限公司 | High-polylactic acid-content film and preparation method thereof |
| CN106674923A (en) * | 2016-12-13 | 2017-05-17 | 常州绿之源高分子材料有限公司 | Controllable-degradation PBAT/PLA (poly(butyleneadipate-co-terephthalate)/polylactic acid) composite film and preparation method thereof |
| CN106750253A (en) * | 2016-12-13 | 2017-05-31 | 常州绿之源高分子材料有限公司 | A kind of PBAT/PLA blendings bulking agent and preparation method thereof |
| CN106751568A (en) * | 2016-12-13 | 2017-05-31 | 常州绿之源高分子材料有限公司 | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof |
| CN106751568B (en) * | 2016-12-13 | 2018-07-13 | 常州绿之源高分子材料有限公司 | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof |
| CN106750253B (en) * | 2016-12-13 | 2018-11-02 | 常州绿之源高分子材料有限公司 | Bulking agent and preparation method thereof is blended in a kind of PBAT/PLA |
| CN106916421A (en) * | 2017-04-07 | 2017-07-04 | 常州大学 | One kind enhancing is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）Ester degradable material |
| CN107118309A (en) * | 2017-06-26 | 2017-09-01 | 浙江海轩科技有限公司 | A kind of biodegradable polyesters alloy and preparation method thereof |
| WO2019010767A1 (en) * | 2017-07-11 | 2019-01-17 | 河南谷润聚合物有限公司 | Method for synthesizing pbat-pla copolyester by means of copolymerization |
| CN107522987A (en) * | 2017-09-29 | 2017-12-29 | 安徽同利塑胶彩印有限公司 | A kind of food pack and preparation method thereof |
| CN108219406A (en) * | 2017-11-29 | 2018-06-29 | 中国科学院宁波材料技术与工程研究所 | A kind of flame retardant type Based Full-degradable Plastics Film and preparation method thereof |
| CN107955350A (en) * | 2017-12-03 | 2018-04-24 | 山东天野生物降解新材料科技有限公司 | A kind of complete biodegradable drug resistance ground film composition and preparation method thereof |
| CN108003583A (en) * | 2017-12-21 | 2018-05-08 | 苏州星火丰盈环保包装有限公司 | A kind of high tensile complete biodegradable refuse bag production technology |
| CN108102308A (en) * | 2017-12-21 | 2018-06-01 | 苏州星火丰盈环保包装有限公司 | A kind of high-compatibility complete biodegradable refuse bag and preparation method thereof |
| CN108102323A (en) * | 2017-12-21 | 2018-06-01 | 苏州星火丰盈环保包装有限公司 | A kind of complete biodegradable refuse bag and preparation method thereof |
| CN108102307A (en) * | 2017-12-21 | 2018-06-01 | 苏州星火丰盈环保包装有限公司 | A kind of high elongation at tear complete biodegradable refuse bag production technology |
| CN108003575A (en) * | 2017-12-21 | 2018-05-08 | 苏州星火丰盈环保包装有限公司 | A kind of PLA, PBAT and PCL blend refuse bag and preparation method thereof |
| CN108359223A (en) * | 2017-12-27 | 2018-08-03 | 杨红梅 | A kind of biodegradable polymer blend and its application |
| CN108359223B (en) * | 2017-12-27 | 2020-07-14 | 杨红梅 | Biodegradable polyester composition and application thereof |
| CN108912630A (en) * | 2018-06-08 | 2018-11-30 | 黑龙江鑫达企业集团有限公司 | A kind of easily peelable environment-friendlythin thin film and its technique for adsorbing bamboo chopsticks |
| CN108912630B (en) * | 2018-06-08 | 2020-10-09 | 黑龙江鑫达企业集团有限公司 | Easily-stripped environment-friendly film and process for adsorbing bamboo chopsticks by using same |
| CN110894344A (en) * | 2018-09-12 | 2020-03-20 | 上海昶法新材料有限公司 | Papermaking waste modified antibacterial degradable garbage bag and preparation method thereof |
| CN109679074A (en) * | 2018-11-30 | 2019-04-26 | 中粮集团有限公司 | A kind of polylactic acid poly shares compound stabilizer and application thereof and application method |
| CN109762307A (en) * | 2018-12-20 | 2019-05-17 | 上海昶法新材料有限公司 | A kind of dedicated antibacterial matrices of biodegradable garbage bag and preparation method thereof |
| CN109825048B (en) * | 2019-02-20 | 2021-03-30 | 华南理工大学 | PLA/PBAT composite material and preparation method thereof |
| CN109825048A (en) * | 2019-02-20 | 2019-05-31 | 华南理工大学 | A kind of PLA/PBAT composite material and preparation method |
| CN110283438A (en) * | 2019-07-22 | 2019-09-27 | 中国科学院长春应用化学研究所 | A kind of base resin and blow molding degradable films of blow molding degradable films |
| CN110499009A (en) * | 2019-08-26 | 2019-11-26 | 青岛嘉泽包装有限公司 | A kind of application of degradable bracing wire basement membrane and preparation method in dismounting bracing wire |
| CN110845830B (en) * | 2019-11-13 | 2022-04-26 | 青岛润兴塑料新材料有限公司 | Starch filled PLA/PBAT full-biodegradable composite material and preparation method thereof |
| CN110845830A (en) * | 2019-11-13 | 2020-02-28 | 青岛润兴塑料新材料有限公司 | Starch filled PLA/PBAT full-biodegradable composite material and preparation method thereof |
| CN113045836A (en) * | 2019-12-28 | 2021-06-29 | 合肥杰事杰新材料股份有限公司 | Degradable high impact polystyrene resin and preparation method thereof |
| CN113045836B (en) * | 2019-12-28 | 2023-11-03 | 合肥杰事杰新材料股份有限公司 | Degradable high-impact polystyrene resin and preparation method thereof |
| CN111073232A (en) * | 2019-12-30 | 2020-04-28 | 武汉华丽环保科技有限公司 | Reinforced filling type full-biodegradable plastic film and preparation method thereof |
| CN111976244A (en) * | 2020-08-31 | 2020-11-24 | 无锡纯宇环保制品有限公司 | Full-biodegradable bubble film composite material and preparation method thereof |
| CN112341763A (en) * | 2020-09-11 | 2021-02-09 | 喀什中天节水科技有限公司 | PBAT composite material film and preparation method and application thereof |
| CN112210195A (en) * | 2020-10-10 | 2021-01-12 | 莱涤新材料(宁波)有限公司 | Biodegradable polylactic acid plastic bag and preparation method thereof |
| CN112662147A (en) * | 2020-12-23 | 2021-04-16 | 青岛润兴塑料新材料有限公司 | High-performance ternary compound biodegradable film |
| CN112679928A (en) * | 2020-12-28 | 2021-04-20 | 东莞市三至新材料技术有限公司 | Full-biodegradable antibacterial PLA/PBAT film and preparation method thereof |
| WO2022177514A1 (en) * | 2020-12-31 | 2022-08-25 | Gema Elektro Plastik Ve Elektronik San. Dis Tic. A. S. | A polymer composition having inorganic additive and production method thereof |
| CN112826299A (en) * | 2021-03-09 | 2021-05-25 | 无锡方成包装科技股份有限公司 | Biodegradable coated paper straw with reinforcing ribs and preparation method thereof |
| CN113429759A (en) * | 2021-07-13 | 2021-09-24 | 山东瑞丰高分子材料股份有限公司 | PBAT composite modified biodegradable material and preparation method thereof |
| CN113480838A (en) * | 2021-07-30 | 2021-10-08 | 宜兴西工维新科技有限公司 | PLA/PBAT film capable of being rapidly degraded and preparation method thereof |
| CN113831708A (en) * | 2021-09-13 | 2021-12-24 | 江西省萍乡市轩品塑胶制品有限公司 | Full-biodegradable film containing coal gangue and preparation method thereof |
| CN114369346A (en) * | 2021-11-30 | 2022-04-19 | 苏州星火丰盈环保包装有限公司 | Biodegradable plastic garbage bag and preparation method thereof |
| CN114230987A (en) * | 2022-01-11 | 2022-03-25 | 南通富士美帽业有限公司 | Environment-friendly high-transparency composite material capable of being sewn and preparation method thereof |
| CN114524958A (en) * | 2022-03-16 | 2022-05-24 | 万华化学集团股份有限公司 | Preparation method of degradable barrier film |
| CN114524958B (en) * | 2022-03-16 | 2023-05-30 | 万华化学集团股份有限公司 | Preparation method of degradable barrier film |
| CN115160740A (en) * | 2022-06-10 | 2022-10-11 | 上海昶法新材料有限公司 | Bio-based fully-degradable controllable agricultural film and preparation method thereof |
| CN115466491A (en) * | 2022-10-09 | 2022-12-13 | 合肥工业大学 | High-modulus degradable PBAT/PLA compound and preparation method thereof |
| CN115558139A (en) * | 2022-10-11 | 2023-01-03 | 福建凯基高分子材料股份有限公司 | Preparation process of antibacterial puncture-resistant PBAT composite film |
| CN115558139B (en) * | 2022-10-11 | 2024-01-26 | 福建凯基高分子材料股份有限公司 | Preparation process of antibacterial penetration-resistant PBAT composite film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103589124B (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103589124A (en) | Fully-biodegradable PLA/PBAT composite film and making method thereof | |
| CN106519618B (en) | A kind of high-content polylactic acid film and preparation method thereof | |
| CN104119647B (en) | A kind of high-content of starch complete biodegradable composition and preparation method thereof | |
| CN103992517B (en) | One can be continuously produced fully-degradable starch base plastic alloy and preparation method thereof | |
| CN107022178A (en) | A kind of biodegradable polylactic acid environment-friendlythin thin film and preparation method thereof | |
| CN103087488B (en) | Biodegradable polylactic acid composite material, and preparation method and application thereof | |
| CN103013070B (en) | Polylactic acid composite material and preparation method thereof | |
| CN103627153A (en) | Entire biodegradation PLA/PBAT composite material and preparing method therefor | |
| CN103265798B (en) | Poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof | |
| CN106433047A (en) | High-strength and high-toughness biodegradable film and preparation method thereof | |
| CN113845621B (en) | Compatibilizer and high-starch-content full-biodegradable film adopting compatibilizer | |
| CN103589125B (en) | A kind of Polylactic acid/polypropylene blend and preparation method thereof | |
| CN107619584A (en) | Lactic acid composite material, tableware and preparation method thereof | |
| CN101875764B (en) | Formable polylactic resin composition and preparation method for plastic strip thereof | |
| CN102070880A (en) | Biodegradable resin composition and product thereof | |
| CN102702705A (en) | Toughened polylactic acid/polyolefin elastomer composite material and preparation method thereof | |
| CN103694646A (en) | Polyester/thermoplastic starch biodegradable composition and preparation method thereof | |
| CN103965516A (en) | Fully biodegradable masterbatch and preparation method thereof | |
| CN102321287B (en) | Biodegradable polyethylene thin film and preparation method thereof | |
| CN101469111A (en) | Wholly-degradable biological plastic poly(3-hydroxybutyrate 4-hydroxybutyrate copolymer) and plant fibre blending alloy | |
| CN106467657A (en) | High heat-resisting PLA/PHA composite and preparation method thereof | |
| CN107841102A (en) | A kind of biodegradable toughness reinforcing heat-proof polylactic acid modified resin and preparation method thereof | |
| CN108017887A (en) | A kind of PLA-PBSA inflation films and preparation method thereof | |
| CN113956630A (en) | Completely biodegradable film and preparation method thereof | |
| CN110317406A (en) | A kind of biodegradable polypropene composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |