CN108929527A - A kind of PBAT/ modified starch full-biodegradable film and its preparation method and application having both high ductibility and high obstructing performance - Google Patents
A kind of PBAT/ modified starch full-biodegradable film and its preparation method and application having both high ductibility and high obstructing performance Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
- B29B7/92—Wood chips or wood fibres
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
-
- 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
Abstract
The invention belongs to modified starch technical fields, disclose a kind of PBAT/ modified starch full-biodegradable film and its preparation method and application for having both high ductibility and high obstructing performance.Preparation method of the present invention the following steps are included: by starch, plasticizer be in mass ratio 6:4~8:2 premixing, obtain premix, add multicomponent organic acid mixing, squeeze out A be granulated, obtain acidified modified thermoplastic starch；PBAT/AMTPS blend is prepared by twin-screw blending extrusion B with PBAT again, PBAT/ modified starch full-biodegradable film is prepared by extrusion-blowfilm shaping, both there is good processing performance, good mechanical property, fracture elongation is promoted to 1000~1400%, and barrier properties for gases is good, gas transmission coefficient is down to 5.6 × 10‑9cm3·cm·cm‑2·s‑1·Pa‑1, can be applied to the fields such as food packaging, mulch and refuse bag.
Description
Technical field
The invention belongs to modified starch technical field, in particular to a kind of high ductibility and high obstructing performance of having both
PBAT/ modified starch full-biodegradable film and its preparation method and application.
Background technique
Starch has many advantages, such as that cheap, easy processing is modified, biodegradability is good, with other biological degradation high score
Sub- material is blended, and can reduce the cost of material, and improve the biodegradability of blend.Polybutylene terephthalate-oneself
The molecular chain structure unit of diacid butanediol copolyester (PBAT) has ester bond and more methylene and aromatic rings, assigns it jointly
Feature with flexibility and rigidity, especially has excellent ductility and toughness, is degradation most popular currently on the market
One of plastics have wide application prospect in biodegradable field of membrane material.However, PBAT film there is high production cost and
The defects such as degradation rate is low, greatly limit it and further apply.Therefore, PBAT can be effectively reduced using PBAT and starch blending
Cost and raising degradation rate.But the poor compatibility of starch and PBAT, with the increase of content of starch, the power of blend film
It learns performance and fierce decline phenomenon occurs, limit application of the PBAT in biodegradation material field.
It is a kind of method for effectively improving film performance by modified with organic acids PBAT/TPS film.Olivato et al.
The type and content that [Carbohydrate Polymers, 2012,90 (1): 159-164.] report organic acid forms sediment to PBAT/
The influence of the mechanical property of powder film.The result shows that starch/PBAT film mechanical property and kinds of organic acids and content are close
It is related.Organic acid promotes dispersion of the starch in PBAT, improves the interface binding power between starch and PBAT.Adding simultaneously
During work, hydrolysis occurs for organic acid and starch, reduces the molecular weight of starch, improves the compatibility of two-phase.Also,
Organic acid has plasticization to blend, weakens its intermolecular force, increases its plasticity.Garcia et al.
[Industrial Crops&Products, 2014,52 (1): 305-312.] are reported using citric acid (CA) as increase-volume
Agent, sodium hypophosphite (SHP) are used as catalyst, prepare modified starch/PBAT film by extrusion-blown modling.With unmodified starch/
PBAT film is compared, and CA modified starch/PBAT film tensile strength increases to 3.8MPa from 2.6MPa, and numerical value rises
47.1%.Lange J et al. [Packaging Technology&Science, 2003,16 (4): 149-158.] is reported
The barrier property of PBAT is poor, and therefore, it is difficult to apply in packing articles.And by modified with organic acids prepare high obstructing performance and
The method of mechanical property yet there are no document report.
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 one kind has both Gao Yan
The preparation method of the PBAT/ modified starch full-biodegradable film of malleability and high obstructing performance.The method of the present invention is first prepared
And low melt viscosity, environmental-friendly acidified modified thermoplastic starch, then with PBAT blending extrusion, obtaining has nano-dispersed ruler
Modified starch is spent, the acidified modified PBAT/TPS film of isotropy and low cost is prepared.
Another object of the present invention be to provide above method preparation have both high ductibility and the PBAT/ of high obstructing performance changes
Property starch full-biodegradable film.Film of the present invention is full-biodegradable film, has excellent ductility, mechanical property and resistance
Separating performance.
Still a further object of the present invention, which is to provide, above-mentioned has both high ductibility and the PBAT/ modified starch of high obstructing performance is given birth to entirely
Application of the object degradable film in the fields such as food packaging, mulch and refuse bag.
The purpose of the present invention is realized by following proposal:
A kind of preparation method for the PBAT/ modified starch full-biodegradable film having both high ductibility and high obstructing performance,
The following steps are included: being in mass ratio 6:4~8:2 premixing by starch, plasticizer, premix is obtained, adding polynary has
Machine acid-mixed is closed, and is squeezed out A and is granulated, obtains acidified modified thermoplastic starch (AMTPS)；Pass through twin-screw blending extrusion B with PBAT again
PBAT/AMTPS blend is prepared, PBAT/ modified starch full-biodegradable film is prepared by extrusion-blowfilm shaping.
The plasticizer can be at least one of water, glycerol, urea, ethylene glycol, sorbierite.
The preparation process of the acidified modified thermoplastic starch of the present invention squeezes out effect, institute to improve acidizing effect and thermoplastic
Mass ratio with plasticizer and starch is preferably 3:7.
The multicomponent organic acid can for succinic acid, malic acid, tartaric acid, citric acid, congealed fat acid and cinnamic acid in extremely
Few one kind.The present invention uses environmental-friendly multicomponent organic acid, reduces environmental pollution.
The dosage of the multicomponent organic acid is the 0.1~8% of starch quality.
The acidified modified thermoplastic starch, PBAT mass ratio be 0.5:9.5~4.5:5.5, preferably 3:7.
The screw speed for squeezing out A is preferably 70~90 revs/min.
The temperature for squeezing out A is preferably 85~160 DEG C.
The extruding pelletization refers to melt tie rod pelletizing or broken after air-cooled after twin-screw extrusion.
During the method for the present invention, acidified modified thermoplastic starch is acidified modified rear starch, viscosity-average molecular weight decline
It is the 5~50% of initial starch.
In the method for the present invention, the starch is preferably first dried using preceding, more preferably 100~110 DEG C dry 7~
8h。
The temperature for squeezing out B is preferably 110~190 DEG C.
Extrusion-the blowfilm shaping preferably uses single screw rod to squeeze out blown film；The temperature of the extrusion-blowfilm shaping is preferred
It is 150~200 DEG C, blow-up ratio is 2~8, and draw ratio is 1~5.
The present invention also provides the PBAT/ modified starches for having both high ductibility and high obstructing performance that the above method is prepared
Full-biodegradable film with good processing performance, and has good mechanical property, and fracture elongation is promoted to 1000~
1400%, horizontal and vertical tensile strength and elongation are respectively 29.5MPa/23.2MPa, and 998%/967%.Gained film thickness
Homogeneity is high, and film-formability can be good, and film thickness is minimum to can reach 30 μm.Film gas excellent in barrier property of the present invention, gas is through system
Number is by 7.9 × 10-9cm3·cm·cm-2·s-1·Pa-1It is reduced to 5.6 × 10-9cm3·cm·cm-2·s-1·Pa-1.The present invention
Method can effectively overcome pure thermoplastic starch in biological degradation plastics dispersion effect difference and reduce film mechanical performance and
The disadvantage of barrier property etc., and increase the dosage of full-biodegradable film biology base, it can be applied to food packaging, mulch and rubbish
The fields such as rubbish bag.And process is easy, technique is environmentally protective, does not cause any harm and pollution to environment.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) easy processing: thermoplastic starch is after organic multicomponent acid is acidified modified, during extrusion plasticizing, in double spiral shells
Starch molecule amount is made to degrade under the shear action of bar, so that effect is mutually tangled between reducing macromolecular chain, to reduce
The melt viscosity of TPS, extrusion plasticizing effect increase.
(2) PBAT/AMTPS full-biodegradable film has many advantages, such as that isotropy, height are uniform: AMTPS is low because having
Melt viscosity can be dispersed in PBAT matrix with Nano grade, so that PBAT/AMTPS melt viscosity is improved, it can be higher
Blow-up ratio under homogeneous film formation.The AMTPS of Nano grade is uniformly coated by PBAT without occurring under the external forces such as blown film
Distribution of orientations, to obtain mechanical property, optical property and the good full-biodegradable film of film thickness homogeneity.In addition, PBAT/
The elongation of AMTPS film can be up to 1400%, improve 47% than pure PBAT, the performance for obstructing air also improves
20%.
(3) environmentally protective: the present invention is cut using starch and plasticizer and edible organic multicomponent acid as raw material by having
The screw extruder continuous production for cutting plastication has many advantages, such as that cheap, operation is easily controllable, nontoxic and pollution-free,
The additive amount of AMTPS is 30% or more, and in the case that comprehensive performance is without being decreased obviously, the cost of film is reduced and it is biological
Matter content then substantial increase, with good economic efficiency and social benefit.
Detailed description of the invention
Fig. 1 is the viscosity test result of TPS and example 1, the 4 acidified modified thermoplastic starch of gained multicomponent organic acid of example
Figure.
The gas permeability coefficient for the PBAT/AMTPS film that Fig. 2 is PBAT, PBAT/TPS, embodiment 10~12 is prepared respectively
Figure.
Fig. 3 is the surface microscopic topographic figure of PBAT film.
Fig. 4 is the surface microscopic topographic figure of PBAT/TPS film.
Fig. 5 is the surface microscopic topographic figure for the PBAT/AMTPS film that embodiment 12 is prepared into.
The mechanical property figure for the PBAT/AMTPS film that Fig. 6 is PBAT, PBAT/TPS, embodiment 12 is prepared respectively.
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.
Material involved in the following example can be obtained from commercial channel.
Following embodiment is the preparation method of acidified modified rear thermoplastic starch sample (AMTPS).
Embodiment 1:
By starch in 110 DEG C of dry 4h.Starch, glycerine are pre-mixed according to the mass ratio of 7:3 again.Then by 1% (base
In starch quality) tartaric acid in high-speed breakage crusher machine, mix with Starch/glycerine premix, reacted by twin-screw
(125~145 DEG C of extrusion temperature, screw speed is 80 turns/min) are squeezed out, is granulated, obtains acidified modified thermoplastic starch
(AMTPS-1)。
Embodiment 2:
By starch in 110 DEG C of dry 4h.Starch, glycerine are pre-mixed according to the mass ratio of 8:2 again.Then by 2% (base
In starch quality) tartaric acid in high-speed breakage crusher machine, mix with Starch/glycerine premix, reacted by twin-screw
(125~145 DEG C of extrusion temperature, screw speed is 80 turns/min) are squeezed out, is granulated, obtains acidified modified thermoplastic starch
(AMTPS-2)。
Embodiment 3:
By starch in 110 DEG C of dry 4h.Starch, glycerine are pre-mixed according to the mass ratio of 7:3 again.Then by 3% (base
In starch quality) tartaric acid in high-speed breakage crusher machine, mix with Starch/glycerine premix, reacted by twin-screw
(125~145 DEG C of extrusion temperature, screw speed is 80 turns/min) are squeezed out, is granulated, obtains acidified modified thermoplastic starch
(AMTPS-3)。
Embodiment 4:
By starch in 110 DEG C of dry 4h.Starch, glycerine are pre-mixed according to the mass ratio of 7:3 again.Then by 4% (base
In starch quality) tartaric acid in high-speed breakage crusher machine, mix with Starch/glycerine premix, reacted by twin-screw
(125~145 DEG C of extrusion temperature, screw speed is 80 turns/min) are squeezed out, is granulated, obtains acidified modified thermoplastic starch
(AMTPS-4)。
Embodiment 5:
By starch in 110 DEG C of dry 4h.Starch, glycerine are pre-mixed according to the mass ratio of 8:2 again.Then by 1% (base
In starch quality) cinnamic acid in high-speed breakage crusher machine, mix with Starch/glycerine premix, reacted by twin-screw
(125~145 DEG C of extrusion temperature, screw speed is 80 turns/min) are squeezed out, is granulated, obtains acidified modified thermoplastic starch
(AMTPS-5)。
Embodiment 6:
By starch in 110 DEG C of dry 4h.Starch, ethylene glycol are pre-mixed according to the mass ratio of 6:4 again.Then by 4% (base
In starch quality) citric acid in high-speed breakage crusher machine, mix with starch/ethylene glycol premix, reacted by twin-screw
(125~145 DEG C of extrusion temperature, screw speed is 80 turns/min) are squeezed out, is granulated, obtains acidified modified thermoplastic starch
(AMTPS-6)。
Embodiment 7:
By starch in 110 DEG C of dry 4h.Starch, urea are pre-mixed according to the mass ratio of 7:3 again.Then 4% (is based on
Starch quality) malic acid in high-speed breakage crusher machine, mixed with starch/ethylene glycol premix, by twin-screw react squeeze
(125~145 DEG C of extrusion temperature, screw speed is 80 turns/min) out, are granulated, obtain acidified modified thermoplastic starch (AMTPS-
7)。
Embodiment 8:
By starch in 110 DEG C of dry 4h.Starch, sorbierite are pre-mixed according to the mass ratio of 7:3 again.Then by 4% (base
In starch quality) succinic acid in high-speed breakage crusher machine, mix with starch/ethylene glycol premix, reacted by twin-screw
(125~145 DEG C of extrusion temperature, screw speed is 80 turns/min) are squeezed out, is granulated, obtains acidified modified thermoplastic starch
(AMTPS-8)。
The modified starch that embodiment 1 and embodiment 4 are prepared detects, the result is shown in Figure 1, comparative sample thermoplastic starch
Powder (TPS) passes through twin-screw reactive extrursion (extrusion temperature 125~145 by mixing starch, glycerine according to mass ratio 7:3
DEG C, screw speed is 80 turns/min), granulation obtains.Other embodiments result is similar.
Following embodiment is the preparation method of PBAT/AMTPS film.
Embodiment 9:
1 gained AMTPS-1 and PBAT of example is pre-mixed according to the mass ratio of 3:7.It (is squeezed out by twin-screw reactive extrursion
135~175 DEG C of temperature, screw speed is 70 turns/min), it is granulated, inflation film manufacturing machine extrusion-blown modling is then squeezed out using single screw rod and (is squeezed out
145~175 DEG C of temperature, screw speed is 70 turns/min, blow-up ratio 3, draw ratio 3), obtain PBAT/AMTPS film
(PBAT/AMTPS-1)。
Embodiment 10:
2 gained AMTPS-1 and PBAT of example is pre-mixed according to the mass ratio of 2:8.It (is squeezed out by twin-screw reactive extrursion
135~175 DEG C of temperature, screw speed is 70 turns/min), it is granulated, inflation film manufacturing machine extrusion-blown modling is then squeezed out using single screw rod and (is squeezed out
145~175 DEG C of temperature, screw speed is 70 turns/min, blow-up ratio 3, draw ratio 3), obtain PBAT/AMTPS film
(PBAT/AMTPS-2)。
Embodiment 11:
3 gained AMTPS-1 and PBAT of example is pre-mixed according to the mass ratio of 3:7.It (is squeezed out by twin-screw reactive extrursion
135~175 DEG C of temperature, screw speed is 70 turns/min), it is granulated, inflation film manufacturing machine extrusion-blown modling is then squeezed out using single screw rod and (is squeezed out
145~175 DEG C of temperature, screw speed is 70 turns/min, blow-up ratio 3, draw ratio 3), obtain PBAT/AMTPS film
(PBAT/AMTPS-3)。
Embodiment 12:
4 gained AMTPS-1 and PBAT of example is pre-mixed according to the mass ratio of 3:7.It (is squeezed out by twin-screw reactive extrursion
135~175 DEG C of temperature, screw speed is 70 turns/min), it is granulated, inflation film manufacturing machine extrusion-blown modling is then squeezed out using single screw rod and (is squeezed out
145~175 DEG C of temperature, screw speed is 70 turns/min, blow-up ratio 3, draw ratio 3), obtain PBAT/AMTPS film
(PBAT/AMTPS-4)。
Embodiment 13:
5 gained AMTPS-5 and PBAT of example is pre-mixed according to the mass ratio of 2:8.It (is squeezed out by twin-screw reactive extrursion
135~175 DEG C of temperature, screw speed is 70 turns/min), it is granulated, inflation film manufacturing machine extrusion-blown modling is then squeezed out using single screw rod and (is squeezed out
145~175 DEG C of temperature, screw speed is 70 turns/min, blow-up ratio 3, draw ratio 3), obtain PBAT/AMTPS film
(PBAT/AMTPS-5)。
Embodiment 14:
6 gained AMTPS-5 and PBAT of example is pre-mixed according to the mass ratio of 4:6.It (is squeezed out by twin-screw reactive extrursion
135~175 DEG C of temperature, screw speed is 70 turns/min), it is granulated, inflation film manufacturing machine extrusion-blown modling is then squeezed out using single screw rod and (is squeezed out
145~175 DEG C of temperature, screw speed is 70 turns/min, blow-up ratio 3, draw ratio 3), obtain PBAT/AMTPS film
(PBAT/AMTPS-6)。
Embodiment 15:
7 gained AMTPS-7 and PBAT of example is pre-mixed according to the mass ratio of 4:6.It (is squeezed out by twin-screw reactive extrursion
135~175 DEG C of temperature, screw speed is 70 turns/min), it is granulated, inflation film manufacturing machine extrusion-blown modling is then squeezed out using single screw rod and (is squeezed out
145~175 DEG C of temperature, screw speed is 70 turns/min, blow-up ratio 3, draw ratio 3), obtain PBAT/AMTPS film
(PBAT/AMTPS-7)。
Embodiment 16:
8 gained AMTPS-8 and PBAT of example is pre-mixed according to the mass ratio of 3:7.It (is squeezed out by twin-screw reactive extrursion
135~175 DEG C of temperature, screw speed is 70 turns/min), it is granulated, inflation film manufacturing machine extrusion-blown modling is then squeezed out using single screw rod and (is squeezed out
145~175 DEG C of temperature, screw speed is 70 turns/min, blow-up ratio 3, draw ratio 3), obtain PBAT/AMTPS film
(PBAT/AMTPS-8)。
The PBAT/AMTPS film that embodiment 9~12 is prepared is detected, as a result sees Fig. 2~Fig. 6.Comparative sample
PBAT/TPS film (squeezes out temperature by twin-screw reactive extrursion by mixing starch (CS), glycerine according to 7:3 (wt%)
125~145 DEG C of degree, screw speed are 80 turns/min), it is granulated, is then pre-mixed with PBAT according to the mass ratio of 3:7.By double
Spiro rod reaction squeezes out (135~175 DEG C of extrusion temperature, screw speed is 70 turns/min), is granulated, is then blown using single screw rod extrusion
Film machine extrusion-blown modling (145~175 DEG C of extrusion temperature, screw speed is 70 turns/min, blow-up ratio 3, draw ratio 3), obtains
PBAT/TPS film (PBAT/TPS).
The gas permeability coefficient for the PBAT/AMTPS film that Fig. 2 is PBAT and PBAT/TPS and embodiment 10~12 is prepared into
Figure.
Fig. 3~Fig. 5 is film surface microscopic appearance figure, and wherein Fig. 3 is PBAT film, and Fig. 4 is PBAT/TPS film, Fig. 5
The PBAT/AMTPS film being prepared into for embodiment 12.
The mechanical property figure for the PBAT/AMTPS film that Fig. 6 is PBAT and PBAT/TPS and embodiment 12 is prepared into.
As seen from the figure, the PBAT/AMTPS full-biodegradable film that the present invention is prepared has good processing performance,
And there is good mechanical property, fracture elongation is promoted to 1000~1400%, horizontal and vertical tensile strength and elongation
Respectively 29.5MPa/23.2MPa, 998%/967%.Gained film thickness homogeneity is high, and film-formability can be good.PBAT/AMTPS is complete
Biodegradable film barrier properties for gases is good, and gas transmission coefficient is by 7.9 × 10-9cm3·cm·cm-2·s-1·Pa-1It is reduced to
5.6×10-9cm3·cm·cm-2·s-1·Pa-1.The method of the present invention can effectively overcome pure thermoplastic starch to mould in complete biodegradable
Dispersion effect difference in material and the disadvantage for reducing mechanical performance and the barrier property of film etc., and it is raw to increase full-biodegradable film
The dosage of object base can be applied to the fields such as food packaging, mulch and refuse bag.And process is easy, technique is environmentally protective, right
Environment does not cause any harm and pollution.
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 preparation method for the PBAT/ modified starch full-biodegradable film for having both high ductibility and high obstructing performance,
It is characterized in that obtaining premix the following steps are included: be in mass ratio 6:4~8:2 premixing by starch, plasticizer, then plus
Enter multicomponent organic acid mixing, squeezes out A and be granulated, obtain acidified modified thermoplastic starch；Pass through twin-screw blending extrusion B with PBAT again
PBAT/AMTPS blend is prepared, PBAT/ modified starch full-biodegradable film is prepared by extrusion-blowfilm shaping.
High ductibility is had both and the PBAT/ modified starch complete biodegradable of high obstructing performance is thin 2. according to claim 1
The preparation method of film, it is characterised in that: the plasticizer is at least one of water, glycerol, urea, ethylene glycol, sorbierite.
High ductibility is had both and the PBAT/ modified starch complete biodegradable of high obstructing performance is thin 3. according to claim 1
The preparation method of film, it is characterised in that: the mass ratio of plasticizer and starch used is 3:7.
High ductibility is had both and the PBAT/ modified starch complete biodegradable of high obstructing performance is thin 4. according to claim 1
The preparation method of film, it is characterised in that: the multicomponent organic acid is succinic acid, malic acid, tartaric acid, citric acid, congealed fat acid
At least one of with cinnamic acid.
High ductibility is had both and the PBAT/ modified starch complete biodegradable of high obstructing performance is thin 5. according to claim 1
The preparation method of film, it is characterised in that: the dosage of the multicomponent organic acid is the 0.1~8% of starch quality.
High ductibility is had both and the PBAT/ modified starch complete biodegradable of high obstructing performance is thin 6. according to claim 1
The preparation method of film, it is characterised in that: the acidified modified thermoplastic starch, PBAT mass ratio be 0.5:9.5~4.5:
5.5。
High ductibility is had both and the PBAT/ modified starch complete biodegradable of high obstructing performance is thin 7. according to claim 1
The preparation method of film, it is characterised in that: the screw speed for squeezing out A is 70~90 revs/min；It is described squeeze out A temperature be
85~160 DEG C.
High ductibility is had both and the PBAT/ modified starch complete biodegradable of high obstructing performance is thin 8. according to claim 1
The preparation method of film, it is characterised in that: the temperature for squeezing out B is 110~190 DEG C；The temperature of the extrusion-blowfilm shaping is
150~200 DEG C, blow-up ratio is 2~8, and draw ratio is 1~5.
9. a kind of PBAT/ modified starch full-biodegradable film for having both high ductibility and high obstructing performance, it is characterised in that root
It is obtained according to preparation method according to any one of claims 1 to 8.
High ductibility is had both and the PBAT/ modified starch full-biodegradable film of high obstructing performance exists 10. as claimed in claim 9
Application in food packaging, mulch and refuse bag field.
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| CN111100431A (en) * | 2019-12-12 | 2020-05-05 | 杭实科技发展(杭州)有限公司 | Granular full-degradable environment-friendly starch and modified starch masterbatch and production method thereof |
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| CN111234279B (en) * | 2020-03-16 | 2021-04-20 | 华中科技大学 | Water vapor barrier biodegradable polymer film and preparation and application thereof |
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| CN111825967B (en) * | 2020-07-30 | 2021-09-21 | 华南理工大学 | High-folding-resistance polylactic acid/thermoplastic starch composite material and application thereof |
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| CN113736119A (en) * | 2021-10-22 | 2021-12-03 | 北京工商大学 | Preparation method and application of biodegradable antioxidant fruit and vegetable preservative film |
| CN113736119B (en) * | 2021-10-22 | 2022-04-15 | 北京工商大学 | Preparation method and application of biodegradable antioxidant fruit and vegetable preservative film |
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