CN110511544B - Biodegradable breathable composite membrane and preparation method thereof - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08J2403/06—Esters
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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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention relates to the technical field of degradable breathable composite membranes, in particular to a biodegradable breathable composite membrane and a preparation method thereof, wherein the biodegradable breathable composite membrane comprises the following preparation raw materials: PE resin, modified porous starch, PBAT resin, a compatilizer, a lubricant, a weather-resistant agent and an opening agent. The biodegradable breathable composite film provided by the invention is developed by adopting PE and PBAT as matrix resins and utilizing the porous and biodegradable characteristics of modified porous starch, solves the defects of uneven pore diameter, poor breathability, incapability of degrading and the like of the traditional breathable composite film, and can be widely applied to the fields of storage, transportation and the like of fruits and vegetables and seafood.
Description
Technical Field
The invention relates to the technical field of degradable breathable composite membranes, in particular to a biodegradable breathable composite membrane and a preparation method thereof.
Background
In recent years, with the rapid development of logistics industry, fresh fruits, vegetables and seafood are slowly and never possible to enter people's lives, and the preservation technology for prolonging the storage life and shelf life of the fruits, the vegetables and the seafood is more and more mature depending on the preservation technology, and is closely related to a preservation packaging material, namely a breathable composite film.
Traditional ventilated membrane mainly adopts inorganic mineral powder to fill PE material preparation, thereby the ventilative principle utilizes the interface separation between inorganic powder and the resin to form the hole that reaches certain aperture and reach ventilative purpose, this is because the reunion of inorganic powder causes the ventilated membrane aperture to distribute unevenly, add inorganic mineral powder and cause stress concentration easily, cause the ventilated membrane air permeability not good, and traditional ventilated membrane is mostly disposable and can not natural degradation moreover, thereby it causes the pollution to the environment to form white rubbish.
Disclosure of Invention
In order to solve the problems of non-uniform pore diameter, poor air permeability and incapability of degradation of a traditional air permeable membrane in the background art, the invention provides a biodegradable air permeable composite membrane, which comprises the following preparation raw materials: PE resin, modified porous starch, PBAT resin, a compatilizer, a lubricant, a weather-resistant agent and an opening agent.
On the basis of the scheme, the feed further comprises the following raw materials in parts by weight:
on the basis of the scheme, the preparation method of the modified porous starch further comprises the following steps:
s100, adding porous starch and water into a reaction container, and stirring, wherein the water is preferably distilled water, and the stirring is preferably to fully and uniformly stir the porous starch and the water to obtain a starch suspension;
s200, heating the starch suspension to 50-70 ℃ while stirring, wherein the heating mode is preferably water bath heating, the water bath heating is preferably that the starch suspension is transferred into a three-neck flask to be heated while stirring, then acetic anhydride and toluene-4-sulfonic acid are sequentially added to be stirred and reacted, and the stirring after the acetic anhydride and the toluene-4-sulfonic acid are sequentially added is preferably fully stirred and continuously reacted for 0.5-3 h to obtain a reaction product A;
s300, adjusting the pH value of the reaction product A to be 7.1-7.8, actually preferably adjusting the pH value in the step to be anhydrous sodium sulfate and sodium hydroxide, adjusting the temperature to be 50-60 ℃, adding a cross-linking agent, preferably a cross-linking agent CL, and reacting for 2-4 hours to obtain a reaction product B;
s400, adjusting the pH value of the reaction product B to be neutral, washing, drying and crushing to obtain the modified porous starch, wherein in the step, the reagent for adjusting the pH value is preferably monosodium citrate.
On the basis of the scheme, the preparation method of the porous starch further comprises the following steps:
s110, adding cassava native starch and water into a reaction vessel and stirring, wherein the water is preferably distilled water, and the stirring is preferably to fully and uniformly stir the cassava native starch and the water to obtain a suspension;
s120, heating the suspension at the temperature of 40-60 ℃ while stirring to gelatinize the starch to obtain gelatinized starch, wherein the gelatinizing time is preferably 30-60 min, and the heat preservation is preferably carried out for 20-40 min after gelatinization;
s130, freezing the gelatinized starch at the temperature of-5 ℃, wherein the freezing time is preferably 48 h;
s140, taking out the frozen sample, adding acetone, stirring and soaking, wherein the acetone is preferably an acetone solution with the volume concentration of 20%, and continuously stirring for 3-5 hours; and performing rotary evaporation at 50-80 ℃, drying and grinding to obtain the porous starch, wherein the rotary evaporation is preferably performed at 50-80 ℃ in a water bath.
On the basis of the scheme, further, the PE resin is blown film-grade low-density polyethylene (LDPE).
On the basis of the scheme, the PE resin preferably has the melt flow rate of 2.8g/10min and the density of 0.92g/cm3The PE resin of (2) is blown film grade Low Density Polyethylene (LDPE).
On the basis of the scheme, the PBAT resin is poly (butylene adipate terephthalate).
On the basis of the scheme, the PBAT resin is preferably poly (butylene adipate/terephthalate) with the melt flow rate of 2-5 g/10min and the relative biodegradation rate of more than or equal to 90%.
On the basis of the scheme, further, the lubricant is at least one of PE wax, stearic acid and EBS.
On the basis of the scheme, the compatilizer is at least one of POE-g-MAH, PE-g-MAH and EVA-g-MAH; the weather resistant agent is a mixture of an antioxidant 168 and an ultraviolet light absorber UV 531.
On the basis of the scheme, the weight ratio of the antioxidant 168 to the UV531 is (1-5): 1.
on the basis of the scheme, the opening agent is at least one of silica and talcum powder inorganic opening agents.
The invention provides a preparation method of a biodegradable breathable composite membrane, which comprises the following steps:
mixing modified porous starch, PE resin, PBAT resin, a compatilizer, a lubricant, a weather-resistant agent and an opening agent, and discharging to obtain a biodegradable breathable composite membrane mixture;
step two, after the biodegradable breathable composite membrane mixture is subjected to melt blending in an internal mixer, performing melt extrusion in a double-screw extruder to obtain a biodegradable breathable composite membrane modified material;
and step three, adding the biodegradable breathable composite membrane modified material into a film blowing machine for film making to obtain the biodegradable breathable composite membrane.
On the basis of the above scheme, further, in the second step, the operating parameters of the internal mixer are as follows: the banburying temperature is 60-100 ℃, and the screw rotating speed is 150-300 r/min; the working parameters of the double-screw extruder are as follows: the temperature of the first zone is 50-65 ℃, the temperature of the second zone is 60-75 ℃, the temperature of the third zone is 90-110 ℃, the temperature of the fourth zone is 110-130 ℃, the temperature of the fifth zone is 110-120 ℃, the temperature of the die head is 80-100 ℃, the feeding speed is 50-150 r/min, and the rotating speed of the screw is 150-300 r/min.
On the basis of the above scheme, further, in the third step, the working parameters of the film blowing machine are as follows: 60-80 ℃ of feeding section, 110-130 ℃ of middle section, 130-160 ℃ of front section, head temperature: the screw rotation speed is 50-100 r/min at 130-150 ℃.
Compared with the prior art, the biodegradable breathable composite membrane and the preparation method thereof provided by the invention have the following technical principles and beneficial effects:
the invention relates to a porous starch, which is a novel starch with a three-dimensional network microstructure with interconnected pores, and the porous starch material is prepared by porous treatment of starch through a cross-linking and freezing combined treatment method, meanwhile, the starch is a natural high polymer material with certain rigidity, hydrogen bonds exist among molecules, the intermolecular force is strong, and the starch has the property of polyhydric alcohol, so that the starch has the characteristics of high viscosity, strong hydrophilic capability, easy gelatinization and the like, and the application of the starch is greatly limited, particularly the application field in the aspect of plastic processing, and the starch is subjected to modification treatment, and the starch hydroxyl is subjected to substitution reaction by adopting acetic anhydride, the reaction temperature is low, the stability of the generated starch acetate is good, the hydrogen bonds among the starch molecules are weakened, a large molecular chain can move at lower temperature, the melting temperature of the starch is reduced, and the thermoplasticity and hydrophobicity of the starch are effectively improved, the hot-melt processability is facilitated, the 'half-cooked' phenomenon of starch in a degradable material is facilitated by reducing the melting temperature of the starch, the thermoplastic property and the hydrophobicity are improved, the compatibility of the starch and matrix resin is facilitated, the uniform molding of the aperture is facilitated, and the stress concentration or interface condition caused by poor compatibility is reduced, so that the application of the starch in the degradable plastic is improved; meanwhile, the addition of the toluene-4-sulfonic acid promotes the esterification reaction of the acetic anhydride and the starch hydroxyl. The invention adopts PE and PBAT as matrix resin, utilizes the porous and biodegradable characteristics of the modified porous starch, adds other processing aids such as compatilizer and lubricant, and develops the biodegradable breathable composite membrane, solves the defects of uneven pore diameter, poor breathable performance, low degradation rate and the like of the traditional breathable composite membrane, and can be widely applied to the fields of storage, transportation and the like of fruits and vegetables and seafood.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM image of a modified porous starch provided by the present invention;
FIG. 2 is an SEM image of a biodegradable gas-permeable composite membrane provided by the present invention;
fig. 3 is an SEM image of a conventional gas permeable composite membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides the following embodiments:
in the following examples and comparative examples, the following preparation starting materials were used for each starting material:
PE resin: type 2426H, blown film grade Low Density Polyethylene (LDPE), melt flow rate of 2.8g/10min, density of 0.92g/cm3Selected from Daqing petrochemical;
PBAT resin: is poly (butylene adipate/terephthalate), type: CZF-06, the melt flow rate is 2-5 g/10min, the relative biodegradation rate is more than or equal to 90%, and the material is selected from Suzhou Hanfeng new materials GmbH;
starch material: cassava starch, type: BEST-2, water content less than or equal to 10%, selected from Sanming Pasteur starch Co.Ltd;
a compatilizer: POE-g-MAH, PE-g-MAH and EVA-g-MAH are all commercial products;
lubricant: PE wax, stearic acid and EBS are commercial products;
weather resisting agent: the mixture of an antioxidant 168 and an ultraviolet light absorber UV531, wherein the weight ratio of the antioxidant 168 to the UV531 is (1-5): 1, and both are commercially available products selected from Guangzhou Yantai chemical company Limited;
an opening agent: the silica opener and talc opener were M-519 and ST-6016, respectively, commercially available products.
Examples 1-5 and comparative examples 1-4:
TABLE 1 summary of the components and proportions of examples 1-5 and comparative examples 1-4
The preparation method comprises the following steps:
preparing porous starch:
(1) weighing 50g of cassava native starch, adding the cassava native starch into a beaker filled with 100mL of distilled water, and fully and uniformly stirring to form a suspension;
(2) pouring the suspension into a reaction kettle, stirring and heating at 50 ℃ to gelatinize the starch for 50min, and keeping the temperature for 30min to obtain gelatinized starch;
(3) directly pouring the gelatinized starch onto a carrying disc of a freeze dryer, putting the gelatinized starch into a refrigerator, and pre-freezing for 48 hours at the temperature of minus 5 ℃;
(4) and taking out the frozen sample, adding 20mL of acetone solution with the volume concentration of 20%, stirring, soaking for 4h, performing rotary evaporation in a water bath at 60 ℃, removing acetone, drying to constant weight, and grinding to obtain the porous starch material.
SEM images of the modified porous starch prepared are shown in FIG. 1.
Preparing modified porous starch:
weighing 200g of the porous starch material prepared above, adding the porous starch material into 400mL of distilled water, fully and uniformly stirring to form a starch suspension, transferring the starch suspension into a 1000mL three-neck flask, heating the starch suspension to 60 ℃ in a water bath while stirring, sequentially adding 5mL of acetic anhydride and 2mL of toluene-4-sulfonic acid, reacting for 1.5h, then adding 10g of anhydrous sodium sulfate and 6g of sodium hydroxide, adjusting the pH value to 7.8, and stirring until the starch suspension is completely dissolved. And finally adding 3g of cross-linking agent CL, reacting for 2h at the temperature of 60 ℃, adding 1.2g of monosodium citrate to adjust the pH value to be neutral, washing, drying and crushing to obtain the modified porous starch.
Preparing a biodegradable breathable composite membrane:
(1) uniformly mixing the prepared modified porous starch with PE resin, PBAT resin, a compatilizer, a lubricant, an antioxidant and an opening agent, and discharging to obtain a biodegradable breathable composite membrane mixture;
(2) carrying out melt blending on the biodegradable breathable composite film mixture in an internal mixer, and carrying out melt extrusion in a double-screw extruder to obtain a biodegradable breathable composite film modified material; the working parameters of the internal mixer are as follows: the banburying temperature is 80 ℃, and the screw rotating speed is 200 r/min; the working parameters of the double-screw extruder are as follows: the temperature of the first zone is 60 ℃, the temperature of the second zone is 75 ℃, the temperature of the third zone is 105 ℃, the temperature of the fourth zone is 115 ℃, the temperature of the fifth zone is 115 ℃, the temperature of the die head is 95 ℃, the feeding speed is 80r/min, and the rotating speed of the screw is 200 r/min;
(3) and adding the biodegradable breathable composite membrane modified material into a film blowing machine for film preparation to obtain the biodegradable breathable composite membrane. The working parameters of the film blowing machine are as follows: feeding section 70 ℃, middle section 115 ℃, front section 145 ℃, head temperature: the screw rotation speed is 60r/min at 130 ℃.
The SEM image of the prepared biodegradable breathable composite membrane is shown in figure 2, while the SEM image of the breathable composite membrane prepared in the prior art is shown in figure 3, and the comparison of the SEM images shows that the biodegradable breathable composite membrane prepared by the invention has more uniform pore diameters.
The specific performance detection and result evaluation are as follows:
the samples obtained in the above examples 1 to 5 and comparative examples 1 to 4 were subjected to a performance test in terms of permeability coefficient according to GB/T1038-2000 "gas permeability test method for Plastic films and sheets-pressure differential method" and aerobic biodegradation rate according to ASTM D6400; the test results are shown in table 2.
TABLE 2 test results of examples 1 to 5 and comparative examples 1 to 4
As can be seen from the results in Table 1, examples 1 to 5 and comparative examples 1 to 4, regardless of whether the examples or comparative examples, the addition of the modified porous starch was effective in increasing O content of the composite film2Permeability coefficient and CO2Air permeability coefficient, the comparative example 1 adopts common cassava starch and O of composite film2Permeability coefficient and CO2The air permeability coefficient is obviously lower than that of the modified porous starch material; comparative examples 2 to 3 were prepared by adding PBAT resin in a large amountCompared with the common cassava starch and the pore-modified starch, the air permeability of the composite membrane is obviously superior to that of the comparative example 3, the aerobic biodegradation rates of the pore-modified starch and the common cassava starch are not greatly different and are obviously lower than those of PBAT resin, and the addition of PBAT can effectively improve the aerobic biodegradation rate of the composite membrane. Comparative example 4, in which no starch material was used, the air permeability was the worst of all the examples and comparative examples, indicating that the addition of modified porous starch effectively improves the air permeability of the composite film. Therefore, the PBAT and the PE are used as matrix resins, and the modified porous starch is added, so that the O content is further improved2Permeability coefficient and CO2The air permeability coefficient and the aerobic biodegradation rate of the composite membrane are improved; in the technical scheme, the biodegradable breathable composite membrane is creatively developed by combining specific preparation methods, the defects that the pore diameter of the holes of the traditional breathable composite membrane is uneven, the breathability is poor, the traditional breathable composite membrane cannot be degraded and the like are overcome, and the biodegradable breathable composite membrane can be widely applied to the fields of storage, transportation and the like of fruits and vegetables and seafood.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The biodegradable breathable composite film is characterized by comprising the following raw materials in parts by weight:
20-40 parts of PE resin;
15-25 parts of modified porous starch;
30-50 parts of PBAT resin;
3-10 parts of a compatilizer;
0.3-2.5 parts of a lubricant;
0.5-3 parts of a weather resistant agent;
0.4-2 parts of an opening agent;
the preparation method of the modified porous starch comprises the following steps:
s100, adding porous starch and water into a reaction container, and stirring to obtain a starch suspension;
s200, heating the starch suspension to 50-70 ℃ while stirring, sequentially adding acetic anhydride and toluene-4-sulfonic acid, stirring and reacting to obtain a reaction product A;
s300, adjusting the pH = 7.1-7.8 of the reaction product A, adjusting the temperature to 50-60 ℃, and adding a cross-linking agent for reaction to obtain a reaction product B;
and S400, adjusting the pH value of the reaction product B to be neutral, washing, drying and crushing to obtain the modified porous starch.
2. The biodegradable breathable composite film according to claim 1, characterized in that: the preparation method of the porous starch comprises the following steps:
s110, adding cassava native starch and water into a reaction vessel and stirring to obtain a suspension;
s120, heating the suspension at the temperature of 40-60 ℃ while stirring to gelatinize the starch to obtain gelatinized starch;
s130, freezing the gelatinized starch at the temperature of-5 ℃;
s140, taking out the frozen sample, adding acetone, stirring, soaking, performing rotary evaporation at 50-80 ℃, drying, and grinding to obtain the porous starch.
3. The biodegradable breathable composite film according to claim 1, characterized in that: the PE resin is blown film-grade low-density polyethylene.
4. The biodegradable breathable composite film according to claim 1, characterized in that: the PBAT resin is poly (butylene adipate terephthalate).
5. The biodegradable breathable composite film according to claim 1, characterized in that: the lubricant is at least one of PE wax, stearic acid and EBS.
6. The biodegradable breathable composite film according to claim 1, characterized in that: the compatilizer is at least one of POE-g-MAH, PE-g-MAH and EVA-g-MAH; the weather resistant agent is a mixture of an antioxidant 168 and an ultraviolet light absorber UV 531.
7. The biodegradable breathable composite film according to claim 1, characterized in that: the opening agent is at least one of silicon dioxide and talcum powder inorganic opening agents.
8. A method of manufacturing a biodegradable breathable composite film according to any one of claims 1-7, characterized in that it comprises the following steps:
mixing modified porous starch, PE resin, PBAT resin, a compatilizer, a lubricant, a weather-resistant agent and an opening agent, and discharging to obtain a biodegradable breathable composite membrane mixture;
step two, after the biodegradable breathable composite membrane mixture is subjected to melt blending in an internal mixer, performing melt extrusion in a double-screw extruder to obtain a biodegradable breathable composite membrane modified material;
and step three, adding the biodegradable breathable composite membrane modified material into a film blowing machine for film making to obtain the biodegradable breathable composite membrane.
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| KR20210070002A (en) * | 2019-12-04 | 2021-06-14 | 한화솔루션 주식회사 | Biodegradable resin compositions and manufacturing methods thereof |
| KR20210070641A (en) * | 2019-12-05 | 2021-06-15 | 한화솔루션 주식회사 | Biodegradable resin compositions and manufacturing methods thereof |
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Denomination of invention: A biodegradable breathable composite membrane and its preparation method Effective date of registration: 20230228 Granted publication date: 20210611 Pledgee: Agricultural Bank of China Limited Mingxi County Sub-branch Pledgor: Fujian Sanming Beststarch Great material Co.,Ltd. Registration number: Y2023350000057 |