CN106751629A - Complete biodegradable preservative film and preparation method thereof - Google Patents
Complete biodegradable preservative film and preparation method thereof Download PDFInfo
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- CN106751629A CN106751629A CN201710053087.2A CN201710053087A CN106751629A CN 106751629 A CN106751629 A CN 106751629A CN 201710053087 A CN201710053087 A CN 201710053087A CN 106751629 A CN106751629 A CN 106751629A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Wrappers (AREA)
Abstract
The present invention relates to a kind of complete biodegradable preservative film and preparation method thereof, belong to polymeric material field.Characterized in that, being made up of the component comprising following weight portion：95 5 parts of PLA, 5 95 parts of Biodegradable polyester, 1 10 parts of toughener, 0.1 6 parts of ethylene decomposition absorbent, 1 20 parts of inorganic filler, 0.1 0.8 parts of processing aid.Good toughness of the present invention, energy complete biodegradable, any pollution is not resulted in environment using after discarded, and the preservative film can be decomposed the ethylene gas that fruits and vegetables are discharged during storage by the effect of ethylene decomposition absorbent, greatly improve the fresh-keeping storage time of fruits and vegetables.
Description
Technical field
The present invention relates to a kind of preparation field of macromolecular material, specifically a kind of complete biodegradable preservative film and its
Preparation method.
Background technology
It is well known that the conventional plastic sheeting of preserving fruit and vegetable utilizing is using materials such as polyethylene, polypropylene, polyvinyl chloride at present
Be prepared from, the equal non-degradable of these materials, and fruit-vegetable plastic wrap is typically all single use, using it is complete it is discarded after be also difficult to
Recycling, easily causes serious pollution to environment.
Biodegradation material such as PLA（PLA）, poly butylene succinate（PBS）, poly-succinic adipic acid butanediol
Ester（PBSA）, it is poly-（Terephthalic acid (TPA) butanediol-co- adipic acid butanediols）Ester（PBAT）, PHA（PHA）Deng all belonging to
In Biodegradable Polymers, it is discarded into nature after this kind of materials'use is complete, can be under nature microorganism effect
It is final to be all degraded to H2O and CO2；If preparing fruit-vegetable plastic wrap with biodegradation material, there is protection well to make to environment
With.But the preservative film being directly prepared into using biodegradation material still suffers from more problem when in use, such as preservative film
Barrier properties for gases, the permeability of vapor etc. are undesirable, fresh-keeping food is easily addled.In addition, fruits and vegetables are in freshness protection package
Interior constantly to discharge ethylene gas, ethylene gas are the ripeners of fruits and vegetables, if ethylene gas fruits and vegetables not discharged
Effectively removal, it will greatly shorten the fresh keeping time of fruits and vegetables.
The content of the invention
In order to overcome the deficiencies in the prior art, the present invention provides a kind of complete biodegradable preservative film and preparation method thereof, tough
Property it is good, can complete biodegradable, any pollution is not resulted in environment using after discarded, and the preservative film can be by ethene
The effect for decomposing absorbent decomposes the ethylene gas that fruits and vegetables are discharged during storage, greatly improves fruits and vegetables
The fresh-keeping storage time.
The technical solution adopted for the present invention to solve the technical problems is：A kind of complete biodegradable preservative film, its feature exists
In being made up of the component comprising following weight portion：95-5 parts of PLA, 5-95 parts of Biodegradable polyester, 1-10 parts of increasing
Tough dose, 0.1-6 parts of ethylene decomposition absorbent, 1-20 parts of inorganic filler, 0.1-0.8 parts of processing aid.
Described PLA number-average molecular weight Mn is 10-30 ten thousand.
Described Biodegradable polyester is poly butylene succinate, poly-succinic tetramethylene adipate, gathers to benzene two
One or more in formic acid butanediol-co- tetramethylene adipates, PHA.
Described toughener is network-like polyester polyols copolymer.
Described ethylene decomposition absorbent be potassium permanganate, silver oxide, rare earth oxide in one or more.
Described inorganic filler be superfine talcum powder, calcium carbonate, montmorillonite, kaolin in one or more.
Described processing aid is the regular processing aids such as lubricant, antioxidant.
A kind of method for preparing foregoing complete biodegradable preservative film, it is characterised in that comprise the following steps：
(1) PLA, Biodegradable polyester are dried into 2-24h in 60-80 DEG C of baking oven, by inorganic filler in 100-120 DEG C of baking
2-4h is dried in case；
(2) each component raw material of following weight portion is weighed by said ratio：PLA 95-5 parts, Biodegradable polyester 5-95 parts,
Toughener 1-10 parts, 0.1-6 parts, inorganic filler 1-20 parts, processing aid 0.1-0.8 parts of ethylene decomposition absorbent；By above-mentioned original
Material is added in high mixer, mixed at high speed 5-10min under normal temperature；
(3) raw material that step (2) is well mixed is added in double screw extruder the melt blending at 120-190 DEG C, extrusion
Modified granulation, obtains preservative film dedicated modified materials；
(4) the preservative film dedicated modified materials that step (3) is obtained are blow molded through Single screw extrusion inflation film manufacturing machine at a temperature of 140-180 DEG C
Film forming, obtains complete biodegradable preservative film；
(5) the complete biodegradable preservative film for obtaining step (4) heat pressure adhesive and cuts into required rule at a temperature of 100-190 DEG C
The Fruit and vegetable preserving bag of lattice.
The beneficial effects of the invention are as follows good toughness, energy complete biodegradable is any using not resulted in environment after discarding
Pollution, and the second that the preservative film can be discharged fruits and vegetables by the effect of ethylene decomposition absorbent during storage
Alkene gas is decomposed, and greatly improves the fresh-keeping storage time of fruits and vegetables.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail
Embodiment 1：
(1) by PLA（NatureWorks companies of the U.S. produce, 4032D）, Biodegradable polyester PBAT（BASF AG gives birth to
Produce, blown film level）24h is dried in 60 DEG C of baking ovens, inorganic filler superfine talcum powder is dried into 4h in 100 DEG C of baking ovens.
(2) each component raw material of following weight portion is weighed by said ratio：95 parts of PLA, Biodegradable polyester PBAT 5
Part, toughener（Produced according to method in embodiment 1 in patent of invention ZL201410662335.X）10 parts, ethylene decomposition absorbent
0.1 part of potassium permanganate, 5 parts of inorganic filler superfine talcum powder, 0.1 part of processing aid lubricant erucyl amide；By above-mentioned raw materials plus
Enter in high mixer, mixed at high speed 5-10min under normal temperature.
(3) raw material that step (2) is well mixed is added in double screw extruder the melt blending at 120-190 DEG C,
The modified granulation of extrusion, obtains preservative film dedicated modified materials.
(4) the preservative film dedicated modified materials for obtaining step (3) through Single screw extrusion inflation film manufacturing machine at a temperature of 140-180 DEG C
Blown Film, obtains complete biodegradable preservative film.
(5) preservative film for obtaining step (4) heat pressure adhesive and cuts into the fruit of required specification at a temperature of 100-190 DEG C
Vegetable freshness protection package.
Embodiment 2：
(1) by PLA（Zhejiang Hai Zheng companies produce, film-grade）, Biodegradable polyester PBS（Anqing and emerging company produce, and blow
Film level）2h is dried in 80 DEG C of baking ovens, inorganic filler calcium carbonate superfine powder is dried into 2h in 120 DEG C of baking ovens.
(2) each component raw material of following weight portion is weighed by said ratio：70 parts of PLA, Biodegradable polyester PBS 30
Part, toughener（Produced according to method in embodiment 1 in patent of invention ZL201410662335.X）6 parts, ethylene decomposition absorbent
4 parts of silver oxide, 10 parts of inorganic filler calcium carbonate superfine powder, 0.3 part of processing aid lubricant stearic acid calcium, antioxidant 1010 0.3
Part；Above-mentioned raw materials are added in high mixer, mixed at high speed 5-10min under normal temperature.
(3) raw material that step (2) is well mixed is added in double screw extruder the melt blending at 120-190 DEG C,
The modified granulation of extrusion, obtains preservative film dedicated modified materials.
(4) the preservative film dedicated modified materials for obtaining step (3) through Single screw extrusion inflation film manufacturing machine at a temperature of 140-180 DEG C
Blown Film, obtains complete biodegradable preservative film.
(5) preservative film for obtaining step (4) heat pressure adhesive and cuts into the fruit of required specification at a temperature of 100-190 DEG C
Vegetable freshness protection package.
Embodiment 3：
(1) by PLA（Shenzhen brilliance great achievement company produces, film-grade）, Biodegradable polyester PBSA（Anqing and emerging company give birth to
Produce, blown film level）3h is dried in 70 DEG C of baking ovens, inorganic filler ultrafine kaolin is dried into 3h in 110 DEG C of baking ovens.
(2) each component raw material of following weight portion is weighed by said ratio：5 parts of PLA, Biodegradable polyester PBSA 95
Part, toughener（Produced according to method in embodiment 1 in patent of invention ZL201410662335.X）1 part, ethylene decomposition absorbent
6 parts of rare earth oxide, 20 parts of inorganic filler ultrafine kaolin, 0.5 part of processing aid lubricant stearic acid calcium, antioxidant 1010
0.3 part；Above-mentioned raw materials are added in high mixer, mixed at high speed 5-10min under normal temperature.
(3) raw material that step (2) is well mixed is added in double screw extruder the melt blending at 120-190 DEG C,
The modified granulation of extrusion, obtains preservative film dedicated modified materials.
(4) the preservative film dedicated modified materials for obtaining step (3) through Single screw extrusion inflation film manufacturing machine at a temperature of 140-180 DEG C
Blown Film, obtains complete biodegradable preservative film.
(5) preservative film for obtaining step (4) heat pressure adhesive and cuts into the fruit of required specification at a temperature of 100-190 DEG C
Vegetable freshness protection package.
Embodiment 4：
(1) by PLA（NatureWorks companies of the U.S. produce, 4032D）, Biodegradable polyester PHA（Tianjin Guo Yun companies give birth to
Produce, blown film level）3h is dried in 70 DEG C of baking ovens, the ultra-fine montmorillonite of inorganic filler is dried into 3h in 105 DEG C of baking ovens.
(2) each component raw material of following weight portion is weighed by said ratio：20 parts of PLA, Biodegradable polyester PHA 80
Part, toughener（Produced according to method in embodiment 2 in patent of invention ZL201410662335.X）5 parts, ethylene decomposition absorbent
5 parts of silver oxide, 1 part of the ultra-fine montmorillonite of inorganic filler, 0.2 part of processing aid lubricant oleamide, 0.3 part of antioxidant 1076；
Above-mentioned raw materials are added in high mixer, mixed at high speed 5-10min under normal temperature.
(3) raw material that step (2) is well mixed is added in double screw extruder the melt blending at 120-190 DEG C,
The modified granulation of extrusion, obtains preservative film dedicated modified materials.
(4) the preservative film dedicated modified materials for obtaining step (3) through Single screw extrusion inflation film manufacturing machine at a temperature of 140-180 DEG C
Blown Film, obtains complete biodegradable preservative film.
(5) preservative film for obtaining step (4) heat pressure adhesive and cuts into the fruit of required specification at a temperature of 100-190 DEG C
Vegetable freshness protection package.
By the banana that the new maturity plucked is 80%, 5kg is respectively taken, be respectively charged into above-described embodiment 1 to phase in embodiment 4
Packaging and tying in the freshness protection package of same specification, store at a temperature of 12-14 DEG C.
Comparative example 1：
By the banana that the new maturity plucked is 80%, 5kg is taken, be fitted into specification size with phase in above-described embodiment 1 to embodiment 4
Packaging and tying in same common polythene freshness protection package, store at a temperature of 12-14 DEG C.
The storage time of different types of fresh-keeping packaging bag see the table below 1 with fresh-keeping effect：
Knowable to the data of table 1, feature complete biodegradable preservative film to be far superior to the fresh-keeping effect of fruits and vegetables it is common can not
The fresh-keeping effect of degrading polyethylene preservative film.
The above-mentioned description to embodiment is to be understood that and apply the present invention for ease of those skilled in the art.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to embodiment here, this
Art personnel announcement of the invention, does not depart from improvement that scope made and modification all should be in the present invention
Protection domain within.
Claims (8)
1. a kind of complete biodegradable preservative film, it is characterised in that be made up of the component comprising following weight portion：95-5 parts of poly- breast
Acid, 5-95 parts of Biodegradable polyester, 1-10 parts of toughener, 0.1-6 parts of ethylene decomposition absorbent, 1-20 parts inorganic are filled out
Material, 0.1-0.8 parts of processing aid.
2. complete biodegradable preservative film according to claim 1, it is characterised in that described PLA number-average molecular weight Mn is
10-30 ten thousand.
3. complete biodegradable preservative film according to claim 1, it is characterised in that described Biodegradable polyester is polybutadiene
Sour butanediol ester, poly-succinic tetramethylene adipate, polybutylene terephthalate-co- tetramethylene adipates, poly- hydroxyl
One or more in alkanoic acid ester.
4. complete biodegradable preservative film according to claim 1, it is characterised in that described toughener is that network-like polyester is more
Membered copolymer.
5. complete biodegradable preservative film according to claim 1, it is characterised in that described ethylene decomposition absorbent is Gao Meng
One or more in sour potassium, silver oxide, rare earth oxide.
6. complete biodegradable preservative film according to claim 1, it is characterised in that described inorganic filler be superfine talcum powder,
One or more in calcium carbonate, montmorillonite, kaolin.
7. complete biodegradable preservative film according to claim 1, it is characterised in that described processing aid is lubricant or anti-
Oxygen agent.
8. a kind of method for preparing complete biodegradable preservative film described in claim 1, it is characterised in that comprise the following steps：
(1) PLA, Biodegradable polyester are dried into 2-24h in 60-80 DEG C of baking oven, by inorganic filler in 100-120 DEG C of baking
2-4h is dried in case；
(2) each component raw material of following weight portion is weighed by said ratio：PLA 95-5 parts, Biodegradable polyester 5-95 parts,
Toughener 1-10 parts, 0.1-6 parts, inorganic filler 1-20 parts, processing aid 0.1-0.8 parts of ethylene decomposition absorbent；By above-mentioned original
Material is added in high mixer, mixed at high speed 5-10min under normal temperature；
(3) raw material that step (2) is well mixed is added in double screw extruder the melt blending at 120-190 DEG C, extrusion
Modified granulation, obtains preservative film dedicated modified materials；
(4) the preservative film dedicated modified materials that step (3) is obtained are blow molded through Single screw extrusion inflation film manufacturing machine at a temperature of 140-180 DEG C
Film forming, obtains complete biodegradable preservative film；
(5) the complete biodegradable preservative film for obtaining step (4) heat pressure adhesive and cuts into required rule at a temperature of 100-190 DEG C
The Fruit and vegetable preserving bag of lattice.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710053087.2A CN106751629A (en) | 2017-01-24 | 2017-01-24 | Complete biodegradable preservative film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710053087.2A CN106751629A (en) | 2017-01-24 | 2017-01-24 | Complete biodegradable preservative film and preparation method thereof |
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Family
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019000588A1 (en) * | 2017-06-29 | 2019-01-03 | 宋梁峰 | Degradable preservative film |
| CN109401225A (en) * | 2018-10-12 | 2019-03-01 | 广东华腾生物有限公司 | A kind of biodegradable preservative film and preparation method thereof |
| CN111040395A (en) * | 2019-05-24 | 2020-04-21 | 包头稀土研究院 | Reinforced and toughened composite material and preparation method thereof |
| CN111959037A (en) * | 2020-08-10 | 2020-11-20 | 广东开放大学（广东理工职业学院） | Complete sets is made to full biodegradable environmental protection bag blown film china ink printing system bag |
| CN113442540A (en) * | 2021-06-25 | 2021-09-28 | 贵州省材料产业技术研究院 | Biodegradable film material and preparation method and application thereof |
| CN113980440A (en) * | 2021-11-23 | 2022-01-28 | 江林（贵州）高科发展股份有限公司 | Biodegradable modified atmosphere preservation box and preparation method and application thereof |
| CN115772322A (en) * | 2021-09-06 | 2023-03-10 | 大禾科技发展(南京)有限公司 | Preparation method of degradable preservative film |
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| CN103059529A (en) * | 2013-01-17 | 2013-04-24 | 山东省意可曼科技有限公司 | Biodegradable preservative film material and preservative film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019000588A1 (en) * | 2017-06-29 | 2019-01-03 | 宋梁峰 | Degradable preservative film |
| CN109401225A (en) * | 2018-10-12 | 2019-03-01 | 广东华腾生物有限公司 | A kind of biodegradable preservative film and preparation method thereof |
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| CN111040395A (en) * | 2019-05-24 | 2020-04-21 | 包头稀土研究院 | Reinforced and toughened composite material and preparation method thereof |
| CN111040395B (en) * | 2019-05-24 | 2022-04-05 | 包头稀土研究院 | Reinforced and toughened composite material and preparation method thereof |
| CN111959037A (en) * | 2020-08-10 | 2020-11-20 | 广东开放大学（广东理工职业学院） | Complete sets is made to full biodegradable environmental protection bag blown film china ink printing system bag |
| CN113442540A (en) * | 2021-06-25 | 2021-09-28 | 贵州省材料产业技术研究院 | Biodegradable film material and preparation method and application thereof |
| CN115772322A (en) * | 2021-09-06 | 2023-03-10 | 大禾科技发展(南京)有限公司 | Preparation method of degradable preservative film |
| CN113980440A (en) * | 2021-11-23 | 2022-01-28 | 江林（贵州）高科发展股份有限公司 | Biodegradable modified atmosphere preservation box and preparation method and application thereof |
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Application publication date: 20170531 |