CN112552654B - PBAT/PHA/wood flour composition suitable for preparing film and preparation and application thereof - Google Patents
PBAT/PHA/wood flour composition suitable for preparing film and preparation and application thereof Download PDFInfo
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- CN112552654B CN112552654B CN202011286982.7A CN202011286982A CN112552654B CN 112552654 B CN112552654 B CN 112552654B CN 202011286982 A CN202011286982 A CN 202011286982A CN 112552654 B CN112552654 B CN 112552654B
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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
-
- 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
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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
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
Abstract
The invention discloses a PBAT/PHA/wood flour composition suitable for preparing a film, and preparation and application thereof in preparing the film, wherein the raw material composition of the composition comprises a basic component and an additional component; the basic components comprise the following components in parts by weight: 30-80 parts of PBAT, 5-30 parts of PHA and 5-40 parts of wood powder; the additional components include, based on the total weight of the base component: 1 to 20 weight percent of plasticizer, 1 to 10 weight percent of compatilizer, 0.1 to 1 weight percent of chain extender, 0.1 to 2 weight percent of lubricant and 0.1 to 1 weight percent of hydrolytic inhibitor. The preparation method comprises the following steps: uniformly mixing the raw materials according to a ratio, adding the mixture into a double-screw granulator set, extruding and granulating to obtain PBAT/PHA/wood powder particles; the temperature of each section of the double-screw granulator set is 45-200 ℃, and the screw rotating speed is 200-450rpm.
Description
Technical Field
The invention relates to the field of biodegradable film materials, in particular to a PBAT/PHA/wood powder composition suitable for preparing a film, and preparation and application thereof.
Background
Biodegradable plastics are a class of plastics that can be caused to degrade by the action of microorganisms that are present in nature. The ideal biodegradable plastic is non-toxic and harmless after being degraded, and has excellent use performance.
The poly (terephthalic acid) -butylene adipate (PBAT) is completely biodegradable aliphatic-aromatic copolyester, has higher elongation at break of more than 700 percent, good flexibility and processability, is widely applied to plastic flexible packaging at present, but the source of the PBAT is still petrochemical engineering, consumes petroleum resources in the production and processing processes and generates more carbon dioxide emission.
Polyhydroxyalkanoate (PHA) is a kind of intracellular polyhydroxyalkanoate synthesized by many microorganisms, and is a natural high molecular biomaterial. Most monomers of PHAs are 3-hydroxy fatty acids with chain lengths of 3-14 carbon atoms, the side chains R of which are highly variable saturated or unsaturated, linear or branched, aliphatic or aromatic groups. More than 100 different monomers have been reported, but no long-chain PHA consisting of more than 14 carbon atoms has been found. Compared with biological materials such as polylactic acid (PLA) and the like, the PHA structure is diversified, the composition of the PHA can be conveniently changed by changing strains, feeding and fermentation processes, and the diversity of the performance brought by the diversity of the composition structure enables the PHA to have obvious advantages in application.
The PBAT and the PHA are compounded to prepare the film for packaging, so that the biomass source of the composite material can be improved and the use of petroleum resources PBAT can be reduced on the premise of ensuring full biodegradation. The invention discloses a biodegradable polyester composition for shopping bags, as disclosed in the Chinese patent application with publication number CN107936486A, which comprises the following components in parts by weight: 80-120 parts of PBAT, 20-40 parts of biodegradable aliphatic polyester such as PHA and the like, 0.5-5 parts of a compatibilizer and 0-1 part of an antioxidant. The compatibility of aliphatic polyesters such as PBAT, PHA and the like is improved by adding the compatibilizer, and the mechanical property is obviously improved.
For example, the Chinese patent application with the publication number of CN108047658A discloses a biodegradable polyester agricultural mulching film, which comprises the following components in parts by weight: 80-100 parts of PBAT, 20-40 parts of PHA and other biodegradable aliphatic polyesters, 2-10 parts of a compatibilizer and 10-20 parts of a filler. But the filler is a silica-coated butyl rubber powder. As the butyl rubber is an undegradable component, although the material cost of the composition and the mulching film product is reduced, the addition of the undegradable component influences the degradation performance of the material. Therefore, a completely biodegradable and cheap biomass filler is required to be selected in the PBAT/PHA system.
For example, chinese patent application with publication number CN108485219A discloses a method for preparing a new bio-based wood-plastic composite material, which comprises the steps of uniformly mixing 80-100 parts of PHA,20-35 parts of surface modified wood powder, 2.5-4.5 parts of titanium dioxide, 0.5-1.0 part of lubricant, 0.2-0.6 part of plasticizer, 0.5-1.0 part of coupling agent, 0.5-1.0 part of antioxidant dioctadecyl thiodipropionate, 0.3-0.7 part of ultraviolet absorbent and 0.1-0.5 part of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) thioether, adding the mixture into a double-screw extruder, and carrying out melt extrusion granulation to prepare the new bio-based wood-plastic composite material. The material can be completely biodegraded, and cheap natural tree wood powder is adopted, so that the production cost is reduced; the adoption of the chemically modified polyhydroxyalkanoate and the surface modified wood flour is beneficial to the mutual fusion of the two materials, so that the materials have better mechanical properties. However, the material does not indicate whether the material can be used in the field of films, so that the PHA and PBAT are blended, wood flour is used as a filled film-grade completely biodegradable material, the consumption of PBAT from petrochemical sources is reduced, and the cost is reduced.
Disclosure of Invention
In order to improve the biomass content of the PBAT complete biodegradation film, reduce the use of petroleum resources PBAT in the composition and reduce the cost while ensuring the biodegradability, the invention provides a PBAT/PHA/wood flour composition suitable for preparing the film. PBAT/PHA/wood flour completely biodegradable film prepared by blow molding PBAT/PHA/wood flour particles prepared by the PBAT/PHA/wood flour composition formula reduces cost and ensures excellent performance of the film.
A PBAT/PHA/wood flour composition suitable for preparing films, the raw material composition comprises a basic component and an additional component;
the basic components comprise the following components in parts by weight:
30-80 parts of PBAT (poly (butylene adipate terephthalate)),
5-30 parts of PHA (polyhydroxyalkanoate),
5-40 parts of wood powder;
the additional components include, based on the total weight of the base component:
the plasticizer is one or more of diethanolamine, triethanolamine, ethylene glycol, glycerol, tripropylene glycol and sorbitol;
the compatilizer is one or more of ethylene-acrylate-maleic anhydride terpolymer (EMH), ethylene acrylate grafted glycidyl methacrylate (T-GMA), ethylene methyl acrylate grafted glycidyl methacrylate (EMA-GMA), ethylene butyl acrylate grafted glycidyl methacrylate (EBA-GMA), polybutylene succinate grafted glycidyl methacrylate (PBS-g-GMA) and polylactic acid grafted glycidyl methacrylate (PLA-g-GMA);
the chain extender is one or more of KC-3728, ADR-4300-F, ADR-4370-F, ADR-4400 and ADR-4468;
the lubricant is one or more of triglycerol monostearate, triglycerol distearate, pentaerythritol stearate and hardened oil;
the hydrolysis resisting agent is one or more of N, N' -bis (2, 6-diisopropylphenyl) carbodiimide, poly-bis (1, 3, 5-triisopropylphenyl) carbodiimide and polymerized carbodiimide.
According to the invention, the addition amount of PHA and wood flour is increased through the optimized composition and proportion of the PBAT/PHA/wood flour composition, so that the production cost is reduced and the addition amount of biomass of the composition is increased on the premise of ensuring the performance.
In order to enable the composition to be suitable for preparing a film with excellent performance, the invention firstly optimizes the proportion content of each component in a PBAT/PHA/wood flour three-component system, and adds a specific amount and a specific type of functional auxiliary agents such as a plasticizer, a compatilizer, a chain extender, a lubricant, an anti-hydrolysis agent and the like on the basis. Research finds that the specific addition amount and specific types of functional additives are important for preparing a film with excellent comprehensive performance from the PBAT/PHA/wood flour composition, and the functional additives are not necessary.
The plasticizer can plasticize wood flour to ensure that the wood flour has certain plasticity, so that the adding proportion of the wood flour in a composition system can be improved, and the excellent performance of a product is ensured.
Because the solubility parameters of PBAT, PHA and wood flour are greatly different, the direct blending of the PBAT, PHA and wood flour can cause the phase separation of the prepared composite material, so that the completely biodegradable film of the blow-molded PBAT/PHA/wood flour has poor performance, obvious layering occurs, and even the film cannot be formed. The compatilizer of the kind is used in the invention to effectively improve the interface compatibility of PBAT, PHA and wood flour, thereby ensuring that the PBAT/PHA/wood flour complete biodegradable film with better performance is prepared.
On the basis of adding the compatilizer, the chain extender of a specific kind is further added to effectively initiate the chain extension reaction of PHA, so that the interfacial compatibility of PBAT/PHA/wood flour is further improved.
Aiming at the composition system of the invention, the fatty acid ester lubricant is also added to reduce the frictional heat between materials and the thermal degradation of the composition, thereby improving the processing performance of the PBAT/PHA/wood powder composition during granulation.
The addition of the specific hydrolysis resistant agent inhibits the ester bonds of PBAT and PHA from being broken in the thermoplastic processing process, thereby improving the performance.
With the aid of the functional additives, the PBAT/PHA/wood flour composition can still be suitable for preparing high-performance films under the condition of containing higher biomass content.
Preferably, the weight average molecular weight of the PBAT is 50000-80000, and the weight average molecular weight range is found to enable the PBAT/PHA/wood flour completely biodegradable film prepared from the composition to have high flexibility.
It was found that the melt flow rate of the particles during the blow molding process to form films has a large influence on the process stability. Preferably, the melt flow rate of the PBAT under the load of 2.16kg and the temperature of 190 ℃ is 1-10g/10min, which is beneficial to ensuring that the PBAT can stably and continuously blow-molded into films in the blow-molding processing process and simultaneously ensures that the thickness of the films is uniform.
The PBAT preferably has one or more of the grades of C1100, C1200, C2224, BX7011, BX8145 and TH 801T.
Preferably, the tensile strength of the PHA is more than or equal to 25MPa, so that the PBAT/PHA/wood flour completely biodegradable film prepared from the composition has higher tensile strength.
The PHA is preferably one or more of the designations EM10080, EM20010, EM20030, EM40010 and F1005.
Preferably, the wood flour is white or light yellow in color, which can ensure the color and transparency of the prepared film.
Preferably, the mesh number of the wood flour is more than 1000 meshes, so that the dispersibility of the wood flour filler, PBAT, PHA and other auxiliary agents can be ensured.
The wood flour is preferably poplar wood flour.
In the above preferred case, in order to accommodate the high addition of wood flour, the PBAT/PHA/wood flour composition comprises, in parts by weight:
30-70 parts of PBAT (poly (butylene adipate terephthalate)),
10-20 parts of PHA (polyhydroxyalkanoate),
10-30 parts of wood powder;
the additional components comprise, based on the total weight of the base component:
the invention also provides a preparation method of the PBAT/PHA/wood flour composition, which comprises the steps of uniformly mixing the raw materials according to the proportion, adding the mixture into a double-screw granulator set, extruding and granulating to obtain PBAT/PHA/wood flour particles;
the temperature of each section of the double-screw granulator set is 45-200 ℃, and the rotating speed of the screws is 200-450rpm.
The mixture can be stirred and mixed for 5-20min at normal temperature by adopting a high-speed mixer.
The invention also provides PBAT/PHA/wood flour particles prepared by the preparation method of the PBAT/PHA/wood flour composition, the water content is 0.1wt% -0.5wt%, and the melt flow rate under the load of 2.16kg and the temperature of 190 ℃ is 1-3g/10min. Under the condition of the special raw material formula, the PBAT/PHA/wood flour particles with the property characteristics of water content, melt flow rate and the like, which are particularly suitable for the subsequent preparation of PBAT/PHA/wood flour complete biodegradable films, can be prepared by the preparation method.
The invention also provides a preparation method of the PBAT/PHA/wood flour complete biodegradable film, wherein a film blowing machine is used for blowing the PBAT/PHA/wood flour particles into a film;
the temperature of each section of a screw of the film blowing machine is 100-180 ℃, and the temperature of a die head is 130-190 ℃.
The invention also provides the PBAT/PHA/wood flour completely biodegradable film prepared by the preparation method.
The invention also provides application of the PBAT/PHA/wood flour composition in preparing films.
Compared with the prior art, the invention has the main advantages that:
1. the invention provides a PBAT/PHA/wood flour composition and a proportion thereof, PHA and wood flour are added into the PBAT full-degradable composition, so that the proportion of biomass sources is increased while the biodegradability is ensured, and the use of petroleum resources PBAT in the composition is reduced.
2. The invention optimizes the composition and the proportion of PBAT/PHA/wood flour, improves the addition of the wood flour on the premise of ensuring the performance, and further reduces the cost.
3. The preparation method of the PBAT/PHA/wood flour particles is optimized, the water content of the prepared PBAT/PHA/wood flour particles is 0.1-0.5 wt%, the melt flow rate under the load of 2.16kg and the temperature of 190 ℃ is 1-3g/10min, and the film blowing processing is facilitated. The PBAT/PHA/wood flour completely biodegradable film provided by the invention has excellent performance and low cost, and is suitable for various packaging products.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
All the raw materials used in the following examples and comparative examples were commercially available except for the specific ones. The weight average molecular weight of PBAT is 50000-80000, and the melt flow rate under a load of 2.16kg and at 190 ℃ is 1-10g/10min. The tensile strength of PHA is not less than 25MPa. The mesh number of the wood powder is more than 1000 meshes.
PBAT/PHA/wood flour particle performance evaluation mode:
and (3) testing the moisture content of the PBAT/PHA/wood flour particles according to the national standard GB/T6284-2006, and testing the melt flow rate of the PBAT/PHA/wood flour particles according to the national standard GB 3682-2000.
The evaluation mode of the performance of the completely biodegradable film comprises the following steps:
tensile strength, tearing strength, pendulum impact resistance and puncture strength test: and testing according to a corresponding national standard testing method.
And (3) testing tensile property: according to the test of GB/T1040.3-2006, the sample adopts type 2, the length is 150mm, the width is 15mm, and the test speed is 200mm/min. Detecting data of the sample in the longitudinal direction and the transverse direction;
and (3) testing the tearing strength: according to the regulation of GB/T16578.2-2009. Detecting data of the sample in the longitudinal direction and the transverse direction;
pendulum impact resistance: testing according to GB/T8809-2015 standard;
puncture strength: testing according to GB/T10004-2008 standard;
the tensile strength unit is MPa, the elongation at break unit is%, the right-angle tearing force unit is N, the pendulum impact resistance unit is J, and the puncture strength unit is N.
Example 1
A PBAT/PHA/wood flour composition comprising the following raw materials:
PBAT BX8145 weight parts, PHA F1005 10 weight parts, and poplar wood powder 23 weight parts;
based on the total weight of PBAT, PHA and poplar wood flour, 8wt% of triethanolamine, 3wt% of EMH, 0.2wt% of KC-3728, 0.8wt% of triglycerol distearate and 0.1wt% of N, N' -bis (2, 6-diisopropylphenyl) carbodiimide.
Example 2
A PBAT/PHA/wood flour composition comprising the following raw materials:
1200 parts of PBAT C, 20 parts of PHA EM40010 and 25 parts of poplar wood powder;
based on the total weight of PBAT, PHA and poplar wood flour, 7.5wt% of diethanolamine, 2wt% of PBS-g-GMA, 0.2wt% of ADR-4468, 0.3wt% of pentaerythritol stearate and 0.2wt% of poly-bis (1, 3, 5-triisopropylphenyl) carbodiimide.
Example 3
A PBAT/PHA/wood flour composition comprising the following raw materials:
PBAT C1200 weight parts, PHA EM10080 weight parts, poplar wood powder 25 weight parts;
taking the total weight of PBAT, PHA and poplar wood powder as reference, 3.5wt% of trimeric glycerol, 4wt% of EBA-GMA, 0.3wt% of ADR-4400.3 wt%, 0.2wt% of pentaerythritol stearate and 0.3wt% of polymerized carbodiimide UN-03.
Example 4
A PBAT/PHA/wood flour composition comprising the following raw materials:
PBAT BX7011, PHA EM10080 and poplar wood powder 22;
based on the total weight of PBAT, PHA and poplar wood powder, 8wt% of sorbitol, 4wt% of EMH, 0.3wt% of ADR-4370-F, 0.7wt% of triglycerol distearate and 0.2wt% of polycarbodiimide UN-03.
Example 5
PBAT/PHA/wood flour composition comprising the following raw materials:
PBAT C1200 weight parts, PHA EM20030 weight parts, poplar wood powder 30 weight parts;
triglycerol 4.5wt%, T-GMA 3wt%, ADR-4468 0.3wt%, hardened oil 0.2wt%, N' -bis (2, 6-diisopropylphenyl) carbodiimide 0.5wt%, based on the total weight of PBAT, PHA and poplar wood flour.
Example 6
A PBAT/PHA/wood flour composition comprising the following raw materials:
PBAT C1100 weight parts, PHA EM20010 weight parts, and poplar wood powder 20 weight parts;
based on the total weight of PBAT, PHA and poplar wood powder, 3.5wt% of ethylene glycol, 4wt% of EMA-GMA, 0.2wt% of ADR-4300-F, 0.3wt% of hardened oil and 0.25wt% of N, N' -bis (2, 6-diisopropylphenyl) carbodiimide.
Example 7
A PBAT/PHA/wood flour composition comprising the following raw materials:
PBAT C1200 weight parts, PHA EM20030 weight parts, poplar wood powder 15 weight parts;
triglycerol 4.5wt%, T-GMA 2wt%, ADR-4468.3wt%, hardened oil 0.2wt%, N' -bis (2, 6-diisopropylphenyl) carbodiimide 0.4wt%, based on the total weight of PBAT, PHA and poplar wood flour.
Example 8
A PBAT/PHA/wood flour composition comprising the following raw materials:
PBAT BX8145 weight parts, PHA EM20010 weight parts, poplar wood powder 10 weight parts;
taking the total weight of PBAT, PHA and poplar wood powder as reference, 1wt% of diethanolamine, 4wt% of T-GMA, 0.3wt% of KC-3728, 0.7wt% of triglycerol monostearate and 0.5wt% of polymerized carbodiimide UN-03.
Example 9
A PBAT/PHA/wood flour composition comprising the following raw materials:
60 parts of PBAT TH801T, 10 parts of PHA EM40010 parts of poplar wood powder;
based on the total weight of PBAT, PHA and poplar wood powder, glycerol is 6wt%, PHA-g-GMA is 3.5wt%, ADR-4400.2 wt%, pentaerythritol stearate is 0.3wt%, and polymeric carbodiimide UN-03.3 wt%.
Example 10
PBAT/PHA/wood flour composition comprising the following raw materials:
PBAT C2224, PHA F1005 and poplar wood powder 22.5;
based on the total weight of PBAT, PHA and poplar wood powder, the adhesive comprises 10wt% of sorbitol, 1wt% of PBS-g-GMA, 0.5wt% of ADR-4370-F, 1wt% of pentaerythritol stearate and 0.1wt% of polymerized carbodiimide UN-03.
Comparative example 1
A PBAT/PHA/wood flour composition comprising the following raw materials:
PBAT BX7011 weight parts, PHA F1005 32 weight parts, poplar wood powder 42 weight parts;
triethanolamine 0.5wt%, EMH11wt%, KC-3728 wt%, triglycerol distearate 2.5wt%, and N, N' -bis (2, 6-diisopropylphenyl) carbodiimide 2wt%, based on the total weight of PBAT, PHA, and poplar wood flour.
Comparative example 2
A PBAT/PHA composition comprising the following raw materials:
PBAT BX8145 weight parts, PHA F1005 10 weight parts;
EMH3wt%, KC-3728.2 wt%, triglycerol distearate 0.8wt%, N' -bis (2, 6-diisopropylphenyl) carbodiimide 0.1wt%, based on the total weight of PBAT and PHA.
The components shown in examples 1-10 and comparative examples 1-2 were prepared according to the following procedure:
(1) Stirring all the components in a high-speed mixer at normal temperature for 18 minutes;
(2) Extruding and granulating by using a parallel double-screw granulator set to obtain PBAT/PHA/wood flour particles. Wherein, the temperature of each section of the double-screw granulator set is as follows: first zone 70 deg.C, second zone 120 deg.C, third zone 140 deg.C, fourth zone 150 deg.C, fifth zone 150 deg.C, sixth zone 155 deg.C, seventh zone 160 deg.C, eighth zone 165 deg.C, ninth zone 160 deg.C, tenth zone 155 deg.C, and head 150 deg.C; setting the screw rotation speed to 300rpm;
the PBAT/PHA/wood flour particles produced were designated S1-S10 (corresponding to examples 1-10) and B1-B2 (corresponding to comparative examples 1-2), respectively.
(3) Use inflation film manufacturing machine, wherein, each district temperature of inflation film manufacturing machine is: the first zone 120 ℃, the second zone 145 ℃, the third zone 150 ℃, the tee-down 155 ℃, the tee-up 160 ℃, the die-down 160 ℃ and the die-up 165 ℃ are controlled to make the thickness of the completely biodegradable film 60 +/-5 μ M, and the prepared films are respectively marked as M1-M10 (corresponding to examples 1-10) and D1-D2 (corresponding to comparative examples 1-2).
The particles S1 to S10 and B1 to B2 were tested and the results are shown in Table 1 below. The fully biodegradable films M1-M10 and D1-D2 were tested and the results are shown in Table 2 below.
TABLE 1
TABLE 2
The composition of comparative example B1 is outside the scope of the invention; comparative example B2 was without wood flour and plasticizer. As can be seen from the data in Table 1, the moisture content of S1-S10 is less than 0.5wt%, and the stability and quality of the subsequent film blowing processing procedure are not affected by too high moisture content. The melt flow rate of S1-S10 is 1-3g/10min, further ensuring the stability and continuity of processing.
The comparative example B1 has high moisture content and low melt index flow rate, and meanwhile, the phenomena of uneven discharging and strip breakage occur in the granulation process, so that continuous granulation and mass production cannot be realized. The melt flow rate of comparative example B2 was slightly higher, affecting the stability of blown film processing, and the bubble slightly swayed during blown film process, resulting in slightly different sizes of the completely biodegradable film.
The composition of comparative example D1 is outside the scope of the invention; comparative example D2 was without wood flour and plasticizer. As can be seen from the data in Table 2, the comparative example D1 has large differences from M1-M10 and D2 in various properties, and the phenomena of air leakage and bubble breakage frequently occur during the film blowing process, and the film surface is extremely rough, which indicates that the addition amount of the composition of D1 is not suitable for the preparation of PBAT/PHA/wood flour complete biodegradable films.
As can be seen from the data in Table 2, the fully biodegradable films of examples M1 to M10, to which wood flour was added, had slightly deteriorated properties as compared to comparative example D2, but they were within a reasonable range, which is why the functional additives of the present invention, including the plasticizer, act together, so that the films still have good properties at high wood flour contents. Therefore, the PBAT/PHA/wood flour completely biodegradable film disclosed by the invention has excellent performance, and each mechanical property index meets the actual application requirement, so that the film is suitable for various packaging products, and is particularly suitable for various packaging film bags.
Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention defined by the appended claims.
Claims (7)
1. A PBAT/PHA/wood flour composition suitable for use in the preparation of films, wherein the raw material composition is a base component and an additional component;
the base components are as follows in parts by weight:
30-80 parts of PBAT (poly (butylene adipate-co-terephthalate)),
5-30 parts of PHA (polyhydroxyalkanoate),
5-40 parts of wood powder;
based on the total weight of the basic components, the additional components are:
the weight average molecular weight of the PBAT is 50000-80000, and the melt flow rate under the load of 2.16kg and the temperature of 190 ℃ is 1-10g/10min;
the tensile strength of the PHA is more than or equal to 25MPa;
the wood powder is poplar wood powder, the color is white or light yellow, and the mesh number is more than 1000 meshes;
the plasticizer is one or more of diethanolamine, triethanolamine, tripropylene glycol and sorbitol;
the compatilizer is one or more of ethylene acrylate grafted glycidyl methacrylate, ethylene butyl acrylate grafted glycidyl methacrylate, polybutylene succinate grafted glycidyl methacrylate and polylactic acid grafted glycidyl methacrylate;
the chain extender is one or more of KC-3728, ADR-4300-F, ADR-4370-F, ADR-4400 and ADR-4468;
the lubricant is one or more of triglycerol monostearate, triglycerol distearate, pentaerythritol stearate and hardened oil;
the hydrolysis resistant agent is poly-bis (1, 3, 5-triisopropylphenyl) carbodiimide;
the PBAT/PHA/wood flour composition suitable for preparing the film has the water content of 0.1wt% -0.5wt%, and the melt flow rate of 1-3g/10min under the load of 2.16kg and the temperature of 190 ℃.
2. The PBAT/PHA/wood flour composition according to claim 1, wherein the basic components comprise, in parts by weight:
30-70 parts of PBAT (poly (butylene adipate terephthalate)),
10-20 parts of PHA (polyhydroxyalkanoate),
10-30 parts of wood powder;
the additional components comprise, based on the total weight of the base component:
3. the preparation method of the PBAT/PHA/wood flour composition as claimed in claim 1 or 2, characterized in that the raw materials are mixed uniformly according to the proportion and then added into a twin-screw granulator set for extrusion and granulation to obtain PBAT/PHA/wood flour particles;
the temperature of each section of the double-screw granulator set is 45-200 ℃, and the rotating speed of the screws is 200-450rpm.
4. PBAT/PHA/wood flour particles produced by the production method according to claim 3, wherein the PBAT/PHA/wood flour particles have a water content of 0.1 to 0.5 wt.% and a melt flow rate of 1 to 3g/10min at 190 ℃ under a load of 2.16 kg.
5. A method for preparing PBAT/PHA/wood flour complete biodegradable film, characterized in that PBAT/PHA/wood flour particles prepared by the preparation method of claim 3 or PBAT/PHA/wood flour particles of claim 4 are blown into film by a film blowing machine;
the temperature of each section of a screw of the film blowing machine is 100-180 ℃, and the temperature of a die head is 130-190 ℃.
6. A PBAT/PHA/wood flour complete biodegradable film prepared by the preparation method of claim 5.
7. Use of the PBAT/PHA/wood flour composition of claim 1 for the preparation of films.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011286982.7A CN112552654B (en) | 2020-11-17 | 2020-11-17 | PBAT/PHA/wood flour composition suitable for preparing film and preparation and application thereof |
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| KR20210111186A (en) * | 2021-07-30 | 2021-09-10 | 씨제이제일제당 (주) | Biodegradable resin composition, biodegradable film and biodegradable articles using same |
| CN113831704A (en) * | 2021-08-10 | 2021-12-24 | 珠海市三绿实业有限公司 | Biodegradable PHA composite material for 3D printer consumable and preparation method thereof |
| CN113881195A (en) * | 2021-09-30 | 2022-01-04 | 宜宾天亿新材料科技有限公司 | Biodegradable resin composition and preparation method thereof |
| CN115260711B (en) * | 2022-08-12 | 2024-01-05 | 横店集团得邦工程塑料有限公司 | Hydrolysis-resistant high-barrier biodegradable film and preparation method thereof |
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| CN105623214A (en) * | 2016-01-13 | 2016-06-01 | 广州市海珥玛植物油脂有限公司 | Plasticized biodegradable polyester film and preparation method thereof |
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| US8753728B2 (en) * | 2011-12-28 | 2014-06-17 | E I Du Pont De Nemours And Company | Toughened polyester blends |
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| CN105623214A (en) * | 2016-01-13 | 2016-06-01 | 广州市海珥玛植物油脂有限公司 | Plasticized biodegradable polyester film and preparation method thereof |
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