CN110527261A - A kind of high barrier Biodegradable film and the preparation method and application thereof - Google Patents
A kind of high barrier Biodegradable film and the preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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- 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
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- 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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
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- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention belongs to packaging material and agricultural film technical field, a kind of high barrier Biodegradable film and the preparation method and application thereof is disclosed.Its raw material includes the component of following weight percent: epoxidation polylactic acid 10-20%, poly butylene succinate-lactic acid copolymer, 5-10% Biodegradable polyester 60-70%, nanometer of masterbatch 10-20%, anti-hydrolysis agent 0.5-5%, antioxidant 0.1-1%.The degradation property of gained Biodegradable films of the invention is excellent, can degradable, no pollution to the environment, nontoxicity, destruction will not be generated to soil texture.Since nanoparticle is evenly dispersed, epoxidation polylactic acid and Biodegradable polyester etc. form the interpenetrating polymer networks structure of micro- crosslinking and anti-hydrolysis agent is added and antioxidant improves the stability of material, therefore the Biodegradable film barrier property is good, good mechanical performance can be used for the high-end film applications demanding to barrier property such as mulch and packaging film.
Description
Technical field
The invention belongs to packaging material and agricultural film technical field, in particular to a kind of high barrier Biodegradable film
And the preparation method and application thereof.
Background technique
It is well known that petroleum resources are increasingly in short supply now, oil price is constantly soaring, brings to people's daily life, work
Many adverse effects have seriously affected the factor leading to social instability of contention for resource between the development speed and area of social economy.
For a long time, used plastic film based article is all with non-biodegradable such as polyvinyl chloride, polyethylene
Disposable film class manufactured goods made of equal materials, are discarded after being finished as rubbish, and this rubbish needs 200 years or so to be divided
Solution causes after abandoning everywhere and endangers very big " white pollution ".Due to the non-degradable characteristic of petrochemical industry plastics, residual
Plastic damage soil texture, make many good farmland underproduction, soil sandification, river blocking causes flood.
Biodegradable film at present, mainly using the biology drop of the blendings such as starch, polylactic acid, poly-succinic acid-butanediol preparation
Resin blown film is solved, polarity is larger, and it is poor to the barrier property of vapor, it is difficult to meet packaging and agricultural use requirement.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of high barrier
Biodegradable film.
Another object of the present invention is to provide a kind of preparation method of above-mentioned high barrier Biodegradable film.
Still a further object of the present invention is to provide above-mentioned high barrier Biodegradable film in preparing mulch and packaging film
Using.
The purpose of the present invention is realized by following proposal:
A kind of high barrier Biodegradable film, raw material include the component of following weight percent:
By polylactic acid and chain extender prepared by the Reaction extrusion in double screw extruder for the epoxidation polylactic acid；Wherein
The content of the polylactic acid is 90~95wt.%, and the content of the chain extender is 1~5wt.%；The chain extender is preferably
Joncryl 4368；The temperature of each temperature section of double screw extruder independently is 180~190 DEG C.
The Biodegradable polyester is poly terephthalic acid-adipic acid-butanediol copolymer, polycaprolactone and poly- hydroxyl
At least one of butyric acid-hydroxypentanoic acid copolyesters；
The nanometer of masterbatch are nano silica and poly terephthalic acid-adipic acid-butanediol copolymer in double spiral shells
In bar extruder prepared by Reaction extrusion；Wherein the nano silica and poly terephthalic acid-adipic acid-butanediol are copolymerized
The mass ratio of object is 1:6~15, preferably 1:9；The temperature of each temperature section in the double screw extruder independently is 160~
170℃。
The anti-hydrolysis agent is at least one of carbodiimides and polycarbodiimide；
The antioxidant is at least one of antioxidant 1010 and irgasfos 168.
A kind of preparation method of above-mentioned high barrier Biodegradable film, specific steps are as follows:
By epoxidation polylactic acid, poly butylene succinate-lactic acid copolymer, Biodegradable polyester, nanometer of masterbatch, water resistant
It solves agent, antioxidant after mixing, is put into pelletizer pelletizing after being kneaded, melted, squeezed out, being cooled down, preparation biodegrade
Gained Biodegradable resin is finally put into inflation film manufacturing machine blown film and prepares high barrier Biodegradable film by resin.
The temperature when melting is 160~190 DEG C, preferably 180 DEG C；The screw speed of the pelletizer be 130~
170rpm, preferably 150rpm.
Above-mentioned high barrier Biodegradable film is preparing the application in mulch and packaging film.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
The degradation property of gained Biodegradable films of the invention is excellent, can degradable, no pollution to the environment, nontoxicity, no
Destruction can be generated to soil texture.Since nanoparticle is evenly dispersed, epoxidation polylactic acid and Biodegradable polyester etc. form
The interpenetrating polymer networks structure and addition anti-hydrolysis agent and antioxidant of micro- crosslinking improve the stability of material, therefore the life
Object degradable film barrier property is good, good mechanical performance, and it is demanding to barrier property high-end thin to can be used for mulch and preservative film etc.
Film field.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
(U.S. 4032D NatureWorks is public by 90-95wt.% polylactic acid for epoxidation polylactic acid described in the present embodiment
Department) in double screw extruder prepared by 180-190 DEG C of Reaction extrusion with 1-5wt.% chain extender Joncryl 4368.
Nanometer of masterbatch described in the present embodiment be 10wt.% nano silica and 90wt.% poly terephthalic acid-oneself
Diacid-butanediol copolymer (C1200 Germany BASF) 160-170 DEG C of nanometer for squeezing out preparation in double screw extruder is female
Material；
In embodiment high barrier Biodegradable film the preparation method comprises the following steps: using double screw extruder as pelletizer,
And the melting billot cooling extruded using water-cooling pattern.Uniformly mixed raw material is put into pelletizer and is kneaded, melted, squeezed
Out, pelletizing after cooling, prepares Biodegradable resin, finally prepares high barrier Biodegradable film in inflation film manufacturing machine blown film.Wherein,
Melt processing temperature is 180 DEG C, screw speed 150rpm.The biodegradable resin particle size of production are as follows: granularity isLength is 3-4mm, cylindrical particle.
Embodiment 1
Prepare raw material: epoxidation polylactic acid 10%, poly butylene succinate-lactic acid copolymer according to weight percent
(BL100 Mitsubishi chemistry) 8%, poly terephthalic acid-adipic acid-butanediol copolymer (C1200 BASF Aktiengesellschaft)
67.3%, nanometer of masterbatch 12%, polycarbodiimide 2.5%, antioxidant 1010 0.2%.
Embodiment 2
Prepare raw material: epoxidation polylactic acid 15%, poly butylene succinate-lactic acid copolymer according to weight percent
(BL100 Mitsubishi chemistry) 5%, poly terephthalic acid-adipic acid-butanediol copolymer (C1200 BASF Aktiengesellschaft)
65%, nanometer of masterbatch 11.5%, carbodiimides 3.2%, irgasfos 168 0.3%.
The performance of high barrier Biodegradable film obtained by 1 Examples 1 and 2 of table
| Embodiment 1 | Embodiment 2 | Commercially available Biodegradable mulch | |||
| Tensile strength | GB/T 1040.2 | MPa | 26.5 | 32.8 | 18.6 |
| Elongation at break | GB/T 1040.2 | % | 350 | 300 | 185 |
| Steam penetrating capacity | GB/T 1037 | g/(m2·h) | 200 | 350 | 980 |
| Biological decomposition rate | GB/T 19277.1 | % | 100 | 100 | 95 |
Table 1 is the performance parameter of high barrier Biodegradable film obtained by Examples 1 and 2, it can be seen that present invention gained
The mechanical property of Biodegradable film and the more commercially available degradative plastic film of the barrier property of vapor are enhanced.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of high barrier Biodegradable film, which is characterized in that its raw material includes the component of following weight percent:
2. high barrier Biodegradable film according to claim 1, it is characterised in that:
By polylactic acid and chain extender prepared by the Reaction extrusion in double screw extruder for the epoxidation polylactic acid.
3. high barrier Biodegradable film according to claim 2, it is characterised in that:
The content of the polylactic acid is 90~95wt.%, and the content of chain extender is 1~5wt.%；The chain extender is Joncryl
4368；
The temperature of each temperature section of double screw extruder independently is 180~190 DEG C.
4. high barrier Biodegradable film according to claim 1, it is characterised in that:
The Biodegradable polyester is poly terephthalic acid-adipic acid-butanediol copolymer, polycaprolactone and poly- hydroxyl fourth
At least one of acid-hydroxypentanoic acid copolyesters.
5. high barrier Biodegradable film according to claim 1, it is characterised in that:
The nanometer of masterbatch are that nano silica and poly terephthalic acid-adipic acid-butanediol copolymer are squeezed in twin-screw
In machine prepared by Reaction extrusion out.
6. high barrier Biodegradable film according to claim 5, it is characterised in that:
The nano silica and poly terephthalic acid-adipic acid-butanediol copolymer mass ratio are 1:6~15；It is described
The temperature of each temperature section in double screw extruder independently is 160~170 DEG C.
7. high barrier Biodegradable film according to claim 1, it is characterised in that:
The anti-hydrolysis agent is at least one of carbodiimides and polycarbodiimide；
The antioxidant is at least one of antioxidant 1010 and irgasfos 168.
8. a kind of method for preparing any one of claim 1~7 high barrier Biodegradable film, it is characterised in that specific
Step are as follows:
By epoxidation polylactic acid, poly butylene succinate-lactic acid copolymer, Biodegradable polyester, nanometer of masterbatch, resistant to hydrolysis
Agent, antioxidant after mixing, are put into pelletizer pelletizing after being kneaded, melted, squeezed out, being cooled down, and prepare biodegrade tree
Gained Biodegradable resin is finally put into inflation film manufacturing machine blown film and prepares high barrier Biodegradable film by rouge.
9. the preparation method of high barrier Biodegradable film according to claim 8, it is characterised in that:
The temperature when melting is 160~190 DEG C；The screw speed of the pelletizer is 130~170rpm.
10. any one high barrier Biodegradable film is preparing answering in mulch and packaging film according to claim 1~7
With.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111361256A (en) * | 2020-04-08 | 2020-07-03 | 保定茂华塑料制品有限公司 | Biodegradable packaging film special for aviation and preparation method thereof |
| CN111703166A (en) * | 2020-05-26 | 2020-09-25 | 安徽国风塑业股份有限公司 | High-barrier fully biodegradable BOPLA film and preparation method thereof |
| CN112876710A (en) * | 2021-01-18 | 2021-06-01 | 山东阜坤新材料有限公司 | Biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and preparation process thereof |
| CN113524831A (en) * | 2021-08-05 | 2021-10-22 | 中国科学院长春应用化学研究所 | Polylactic acid-based environment-friendly agricultural mulching film and preparation method thereof |
| CN112876860B (en) * | 2021-01-18 | 2022-01-11 | 山东阜坤新材料有限公司 | Biodegradable antistatic graphene in-situ polymerization copolyester cast film and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111361256A (en) * | 2020-04-08 | 2020-07-03 | 保定茂华塑料制品有限公司 | Biodegradable packaging film special for aviation and preparation method thereof |
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| CN112876860B (en) * | 2021-01-18 | 2022-01-11 | 山东阜坤新材料有限公司 | Biodegradable antistatic graphene in-situ polymerization copolyester cast film and preparation process thereof |
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