CN106987107A - A kind of degradable resin composition and degradable resin film - Google Patents
A kind of degradable resin composition and degradable resin film Download PDFInfo
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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
- 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
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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
- C08J2467/02—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention provides a kind of degradable resin composition and degradable resin film, said composition is in terms of parts by weight, including 50~80 parts of PLA, 20~50 parts of hexanedioic acid terephthalic acid (TPA) butanediol copolymer, two 0.5~5 part of hydrocarbon polymers, 0.1~2 part of crosslinking agent and 2,3 0.5~2 part of expoxy propane methacrylates.Said composition uses hexanedioic acid terephthalic acid (TPA) butanediol copolymer, two hydrocarbon polymers and 2, and 3 expoxy propane methacrylates are to polylactic acid modified in the presence of crosslinking agent, and making the resin film of preparation has excellent mechanical property；Higher blown film stability, will not produce drift, the wild effect such as shake, can be used as packaging group product.The longitudinal tensile strength of resin film is 38~61MPa, and longitudinal elongation at break rate is 265~463%；Transverse tensile strength is 32~54MPa, and transverse breakage elongation is 268~538%.
Description
Technical field
The present invention relates to technical field of plastic package, more particularly to a kind of degradable resin composition and degradable resin it is thin
Film.
Background technology
There is plastic film papery to pack and the incomparable advantage of mental package, since appearance, obtain rapidly
Extensive use, is used in terms of food, medicine, clothes, electronic industry.However, the nondegradable characteristic of common plasticses,
So that waste plastic packaging material is treated as problem, current processing mode still based on burning and fill, burns meeting
The pernicious gases such as dioxin are produced, and landfill side's processing mode can occupy large area soil, and partly plastic packaging is with dampening
Soil, which is lost in, to be collected in ocean, causes serious ecocatastrophe.
To solve a series of problems that non-degradable plastic refuse is brought, the concept of degradation plastic is just drawn once proposition
Play industry extensive concern.At present, PLA, hexanedioic acid-terephthalic acid (TPA)-butanediol copolymer, poly butylene succinate, poly-
The degradation plastic industry such as hydroxyalkanoate, polycaprolactone obtains large development.Wherein PLA relies on its excellent mechanics
Performance, relatively low cost have become the maximum degradation plastic of industry size.But in plastics package industry, PLA is higher
Mechanical strength be not suitable for softness packaging applications, therefore for PLA flexible package application and development be always PLA production
Industry major fields.
Patent 201410662335X synthesis is a kind of to be used as toughener, addition to poly- breast by network-like polyester polyols copolymer
In sour matrix resin, the polylactic acid film of toughening modifying is prepared.Patent 2004100414253, by isocyanate-terminated polyethers or
Terminal isocyanate group polyester carries out reaction chain extension with PLA prepolymer, obtains intrinsic toughening type film-grade copolymer of poly lactic acid, should
The many preparations and purification of lactide of method, can reduce product cost.Patent 2007101900638 discloses a kind of poly- breast
Acid/thermoplastic starch extrusion blow molding film and production method, this method technique are simple, are easy to operation, and ensure that product
Degradable characteristic.But the standby thin film mechanical performance of above-mentioned patent system is poor.
The content of the invention
In view of this, should it is an object of the invention to provide a kind of degradable resin composition and degradable resin film
Film has preferable mechanical property.
The invention provides a kind of degradable resin composition, in terms of parts by weight, including following components：
50~80 parts of PLA, hexanedioic acid-terephthalic acid (TPA) -20~50 parts of butanediol copolymer, two hydrocarbon polymers 0.5
~5 parts, 0.1~2 part of crosslinking agent and 0.5~2 part of 2,3- expoxy propane methacrylate.
Preferably, two hydrocarbon polymer is polymerized by two hydrocarbon monomers；
Two hydrocarbon monomer is selected from 1,3- butadiene or 2- methyl isophthalic acids, 3- butadiene.
Preferably, the number-average molecular weight of the PLA is 5 × 104~5 × 105g/mol。
Preferably, the number-average molecular weight of the hexanedioic acid-terephthalic acid (TPA)-butanediol copolymer is 5 × 104~5 ×
105g/mol。
Preferably, the number-average molecular weight of two hydrocarbon polymer is 2000~8000g/mol.
Preferably, the crosslinking agent is selected from cumyl peroxide and/or double tert-butyl peroxide hexanes.
The invention provides a kind of degradable resin composition film, degradable resin is combined described in above-mentioned technical proposal
Thing is granulated, and blow molding is made.
Preferably, the thickness of the degradable resin composition film is 10~50 microns.
Preferably, the temperature of the granulation is 150~200 DEG C.
Preferably, the temperature of the blow molding is 140~180 DEG C.
The invention provides a kind of degradable resin composition, in terms of parts by weight, including following components：PLA 50~
80 parts, hexanedioic acid-terephthalic acid (TPA) -20~50 parts of butanediol copolymer, two 0.5~5 part of hydrocarbon polymers, crosslinking agent 0.1~2
0.5~2 part of part and 2,3- expoxy propane methacrylate.The degradable resin composition that the present invention is provided is by using two
The work of acid-terephthalic acid (TPA)-butanediol copolymer, two hydrocarbon polymers and 2,3- expoxy propane methacrylate in crosslinking agent
With lower to polylactic acid modified, make its degradable resin film prepared that there is excellent mechanical property.In addition, the resin combination
The resin film of preparation also has higher blown film stability, will not produce drift, the wild effect such as shake, can be as packing
Class product is used.Test result indicates that：The longitudinal tensile strength of resin film prepared by the degradable resin composition for 38~
61MPa, and longitudinal elongation at break rate is 265~463%；Transverse tensile strength is 32~54MPa, and transverse breakage elongation is
268~538%.
Embodiment
The invention provides a kind of degradable resin composition, in terms of parts by weight, including following components：
50~80 parts of PLA, hexanedioic acid-terephthalic acid (TPA) -20~50 parts of butanediol copolymer, two hydrocarbon polymers 0.5
~5 parts, 0.1~2 part of crosslinking agent and 0.5~2 part of 2,3- expoxy propane methacrylate.
The degradable resin composition that the present invention is provided is by using hexanedioic acid-terephthalic acid (TPA)-butanediol copolymer, two
Hydrocarbon polymer and 2,3- expoxy propane methacrylate, to polylactic acid modified, make resin combination in the presence of crosslinking agent
The degradable resin film of preparation has excellent mechanical property.In addition, resin film prepared by the resin combination also has
Higher blown film stability, will not produce drift, the wild effect such as shake, can be used as packaging group product.
In the present invention, the degradable resin composition includes 50~80 parts of PLA.The PLA is that have rotation
Photoactive polymer；Present invention preferably employs low polarimetry purity, the PLA of low melting point；Specifically, being preferred to use not higher than
95% PLLA.The number-average molecular weight of the PLA is preferably 5 × 104~5 × 105G/mol, more preferably 1 ×
105~2 × 105g/mol。
In the present invention, degradable resin composition includes hexanedioic acid-terephthalic acid (TPA)-butanediol copolymer (PBAT) 20
~50 parts.The number-average molecular weight of the hexanedioic acid-terephthalic acid (TPA)-butanediol copolymer is preferably 5 × 104~5 × 105g/
mol.In a particular embodiment of the present invention, the number-average molecular weight of the hexanedioic acid-terephthalic acid (TPA)-butanediol copolymer is specific
For 1 × 105g/mol、5×105g/mol、5×104g/mol、2×105G/mol and 4 × 105g/mol。
In the present invention, the degradable resin composition includes 0.5~5 part of two hydrocarbon polymer.Two hydro carbons gathers
The number-average molecular weight of compound is preferably 2000~8000g/mol, more preferably 3000~6000g/mol.Two hydrocarbon-based polymeric
Thing is polymerized by two hydrocarbon monomers；Two hydrocarbon monomer is selected from 1,3- butadiene or 2- methyl isophthalic acids, 3- butadiene.In this hair
In bright specific embodiment, two hydrocarbon polymer is poly- 1,3-butadiene or poly- 2- methyl isophthalic acids, 3- butadiene；Described poly- 1,
The molecular weight of 3- butadiene is preferably specially 7000g/mol, 2000g/mol or 8000g/mol；The poly- 2- methyl isophthalic acids, 3- fourths
The molecular weight of diene is preferably specially 5000g/mol or 2000g/mol.
In the present invention, degradable resin composition includes 0.1~2 part of crosslinking agent.The crosslinking agent is selected from peroxidating two
Isopropylbenzene and/or double tert-butyl peroxide hexanes.The present invention, without special limitation, is adopted to the source of the crosslinking agent of mentioned kind
With mentioned kind well known to those skilled in the art, its commercial goods can be such as used.
In the present invention, degradable resin composition includes 0.5~2 part of 2,3- expoxy propane methacrylate (DCP).
The present invention does not have special limitation to 2, the 3- expoxy propane methacrylate, using well known to those skilled in the art 2,
3- expoxy propane methacrylates, such as use its commercial goods.
Present invention also offers a kind of degradable resin film, degradable resin composition is made as described in above-mentioned technical proposal
Grain, blow molding is made.
Specifically, the preparation method of the degradable resin composition film comprises the following steps：
By PLA, hexanedioic acid-terephthalic acid (TPA)-butanediol copolymer, two hydrocarbon polymers, crosslinking agent and 2,3- epoxies
Propane methacrylate is blended, and granulation, then blow molding obtains degradable resin composition film.
In the present invention, the PLA, hexanedioic acid-terephthalic acid (TPA)-butanediol copolymer, two hydrocarbon polymers, friendship
Join PLA described in agent and consumption, species and the source of 2,3- expoxy propane methacrylates and above-mentioned technical proposal, two
Acid-terephthalic acid (TPA)-butanediol copolymer, two hydrocarbon polymers, the use of crosslinking agent and 2,3- expoxy propane methacrylates
Amount, species are consistent with source, will not be repeated here.
In the present invention, the thickness of the degradable resin composition film is preferably 10~50 microns.
In the present invention, the temperature of the granulation is preferably 150~200 DEG C.The temperature of the blow molding is preferably 140
~180 DEG C.
The invention provides a kind of degradable resin composition, in terms of parts by weight, including following components：PLA 50~
80 parts, hexanedioic acid-terephthalic acid (TPA) -20~50 parts of butanediol copolymer, two 0.5~5 part of hydrocarbon polymers, crosslinking agent 0.1~2
0.5~2 part of part and 2,3- expoxy propane methacrylate.The degradable resin composition that the present invention is provided is by using two
The work of acid-terephthalic acid (TPA)-butanediol copolymer, two hydrocarbon polymers and 2,3- expoxy propane methacrylate in crosslinking agent
With lower to polylactic acid modified, make its degradable resin film prepared that there is excellent mechanical property.In addition, the resin combination
The resin film of preparation also has higher blown film stability, will not produce drift, the wild effect such as shake, can be as packing
Class product is used.Test result indicates that：The longitudinal tensile strength of resin film prepared by the degradable resin composition for 38~
61MPa, and longitudinal elongation at break rate is 265~463%；Transverse tensile strength is 32~54MPa, and transverse breakage elongation is
268~538%.
In order to further illustrate the present invention, a kind of degradable resin composition provided with reference to embodiment the present invention
Can degradable resin film be described in detail, but they can not be interpreted as limiting the scope of the present invention.
Comparative example 1
By 50wt% PLAs (number-average molecular weight 5 × 104G/mol), 50wt% hexanedioic acids-terephthalic acid (TPA)-butanediol
Copolymer (number-average molecular weight 5 × 104G/mol) after height is stirred and mixed 5 minutes in machine, add in double screw extruder, at 170 DEG C
Extruding pelletization.By blending resin, 160 DEG C of blow moldings in inflation film manufacturing machine, obtain resin film；About 25 μm of resin film thickness.
The present invention carries out Mechanics Performance Testing to resin film prepared by comparative example 1, the results are shown in Table 1.
Comparative example 2
By 70wt% PLAs (number-average molecular weight 9 × 104G/mol), 30wt% hexanedioic acids-terephthalic acid (TPA)-butanediol
Copolymer (number-average molecular weight 8 × 104G/mol) after height is stirred and mixed 5 minutes in machine, add in double screw extruder, at 190 DEG C
Extruding pelletization.By blending resin, 180 DEG C of blow moldings in inflation film manufacturing machine, obtain resin film；About 50 μm of the film thickness.
The present invention carries out Mechanics Performance Testing to resin film prepared by comparative example 2, the results are shown in Table 1.
Embodiment 1
By 50wt%PLA (Mn=5 × 104G/mol), 47.4wt%PBAT (Mn=1 × 105G/mol), 2wt%GMA,
The poly- 1,3-butadienes of 0.5wt% (Mn=8000g/mol), 0.1wt%DCP 150 DEG C of blending granulations in double screw extruder, will
Final modified resin blow molding in inflation film manufacturing machine, blown film temperature is 140 DEG C, obtains degradable resin film, the film thickness
For 10 μm.
The present invention carries out Mechanics Performance Testing to resin film prepared by embodiment 1, the results are shown in Table 1.
Embodiment 2
By 80wt%PLA (Mn=1 × 105G/mol), 12wt%PBAT (Mn=5 × 105G/mol), 1wt%GMA,
The poly- 1,3-butadienes of 5wt% (Mn=2000g/mol), 2wt%DCP 180 DEG C of blending granulations in double screw extruder, will be final
Modified resin blow molding in inflation film manufacturing machine, blown film temperature is 160 DEG C, obtains degradable resin film, and the film thickness is 50 μ
m。
The present invention carries out Mechanics Performance Testing to resin film prepared by embodiment 2, the results are shown in Table 1.
Embodiment 3
By 60wt%PLA (Mn=5 × 105G/mol), 22wt%PBAT (Mn=5 × 104G/mol), 1wt%GMA,
The poly- 2- methyl isophthalic acids of 5wt%, 3- butadiene (Mn=2000g/mol), 2wt%DCP 200 DEG C of blendings in double screw extruder are made
Grain, the blow molding in inflation film manufacturing machine by final modified resin, blown film temperature is 170 DEG C, obtains degradable resin film, the film
Thickness is 30 μm.
The present invention carries out Mechanics Performance Testing to resin film prepared by embodiment 3, the results are shown in Table 1.
Embodiment 4
By 70wt%PLA (Mn=2 × 105G/mol), 28.9wt%PBAT (Mn=2 × 105G/mol), 0.5wt%GMA,
The poly- 2- methyl isophthalic acids of 0.5wt%, 3- butadiene (Mn=2000g/mol), 0.1wt%DCP 200 DEG C of blendings in double screw extruder
Granulation, the blow molding in inflation film manufacturing machine by final modified resin, blown film temperature is 170 DEG C, obtains degradable resin film, this is thin
Film thickness is 40 μm.
The present invention carries out Mechanics Performance Testing to resin film prepared by embodiment 4, the results are shown in Table 1.
Embodiment 5
By 60wt%PLA (Mn=8 × 104G/mol), 25.5wt%PBAT (Mn=2 × 105G/mol), 1wt%GMA,
The poly- 2- methyl isophthalic acids of 3wt%, 3- butadiene (Mn=5000g/mol), 0.5wt%DCP 200 DEG C of blendings in double screw extruder are made
Grain, the blow molding in inflation film manufacturing machine by final modified resin, blown film temperature is 170 DEG C, obtains degradable resin film, the film
Thickness is 25 μm.
The present invention carries out Mechanics Performance Testing to resin film prepared by embodiment 5, the results are shown in Table 1.
Embodiment 6
By 50wt%PLA (Mn=3 × 105G/mol), 42wt%PBAT (Mn=4 × 105G/mol), 2wt%GMA,
The poly- 1,3-butadienes of 5wt% (Mn=7000g/mol), 1wt%DCP 190 DEG C of blending granulations in double screw extruder, will be final
Modified resin blow molding in inflation film manufacturing machine, blown film temperature is 170 DEG C, obtains degradable resin film, and the film thickness is 15 μ
m。
The present invention carries out Mechanics Performance Testing to resin film prepared by embodiment 6, the results are shown in Table 1.
The mechanical property result of resin film prepared by the comparative example 1~2 of table 1 and embodiment 1~6
As shown in Table 1, using diacid-terephthalic acid (TPA)-butanediol copolymer, two hydrocarbon polymers and 2,3- expoxy propane
Methacrylate is in the presence of crosslinking agent to polylactic acid modified so that the mechanical property of film is obviously improved.
As seen from the above embodiment, the invention provides a kind of degradable resin composition, in terms of parts by weight, including with
Lower component：50~80 parts of PLA, hexanedioic acid-terephthalic acid (TPA) -20~50 parts of butanediol copolymer, two hydrocarbon polymers 0.5
~5 parts, 0.1~2 part of crosslinking agent and 0.5~2 part of 2,3- expoxy propane methacrylate.The degradable resin that the present invention is provided
Composition is by using hexanedioic acid-terephthalic acid (TPA)-butanediol copolymer, two hydrocarbon polymers and 2,3- expoxy propane methyl-props
Olefin(e) acid ester, to polylactic acid modified, makes its degradable resin film prepared have excellent mechanical property in the presence of crosslinking agent
Energy.In addition, resin film prepared by the resin combination also has higher blown film stability, drift, shake etc. will not be produced
Wild effect, can be used as packaging group product.Test result indicates that：Resin film prepared by the degradable resin composition
Longitudinal tensile strength be 38~61MPa, and longitudinal elongation at break rate be 265~463%；Transverse tensile strength be 32~
54MPa, and transverse breakage elongation is 268~538%.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of degradable resin composition, in terms of parts by weight, including following components：
50~80 parts of PLA, hexanedioic acid-terephthalic acid (TPA) -20~50 parts of butanediol copolymer, two hydrocarbon polymers 0.5~5
Part, 0.1~2 part of crosslinking agent and 0.5~2 part of 2,3- expoxy propane methacrylate.
2. degradable resin composition according to claim 1, it is characterised in that two hydrocarbon polymer is by two hydro carbons
Monomer is polymerized；
Two hydrocarbon monomer is selected from 1,3- butadiene or 2- methyl isophthalic acids, 3- butadiene.
3. degradable resin composition according to claim 1, it is characterised in that the number-average molecular weight of the PLA is
5×104~5 × 105g/mol。
4. degradable resin composition according to claim 1, it is characterised in that the hexanedioic acid-terephthalic acid (TPA)-fourth
The number-average molecular weight of diol copolymer is 5 × 104~5 × 105g/mol。
5. degradable resin composition according to claim 1, it is characterised in that the number of two hydrocarbon polymer is divided equally
Son amount is 2000~8000g/mol.
6. degradable resin composition according to claim 1, it is characterised in that it is different that the crosslinking agent is selected from peroxidating two
Propyl benzene and/or double tert-butyl peroxide hexanes.
7. a kind of degradable resin film, is granulated as degradable resin composition described in claim 1, blow molding is made.
8. degradable resin composition film according to claim 7, it is characterised in that the degradable resin composition
The thickness of film is 10~50 microns.
9. degradable resin composition film according to claim 7, it is characterised in that the temperature of the granulation is 150
~200 DEG C.
10. degradable resin composition film according to claim 7, it is characterised in that the temperature of the blow molding
For 140~180 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112550930A (en) * | 2021-01-04 | 2021-03-26 | 安徽沪通环保包装科技有限公司 | Convenient square-bottom bag and manufacturing method thereof |
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Application publication date: 20170728 |