CN110724295A - Temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane and preparation method thereof - Google Patents
Temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane and a preparation method thereof. A preparation method of a temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane is characterized in that firstly PCL4000, PEG2000, MDI, 1BDO and the like are selected as main raw materials, and TSPU solution is synthesized by a two-step solution block copolymerization technology; natural plant essential oil is used as an antioxidant, and is embedded by a liposome technology for protection and controlled release; and then mixing and casting the TSPU solution and the freeze-dried essential oil freeze-dried liposome to form an inner layer controlled-release base material with an intelligent control function, and finally compounding the base material and an outer layer barrier layer to prepare the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane.
Description
Technical Field
The invention relates to an antioxidant active food packaging material, in particular to a temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite film and a preparation method thereof, belonging to the technical field of intelligent controlled-release active food packaging materials.
Background
In recent years, there has been growing interest in preparing antioxidative packaging materials by incorporating antioxidants into the polymer matrix or coating onto the surface of the polymer film, three forms, ①, by dissolving both in a suitable solvent and then applying the solution to the substrate by coating techniques, ②, by melting the polymer and using extrusion techniques, incorporating and mixing the antioxidant into the melt, ③, immobilizing the antioxidant on the film surface.
Because the migration of synthetic antioxidants may have negative effects on human health, the development of natural antioxidants attracts the extensive attention of researchers, the continuous search for new effective natural antioxidants is one of the important trends in the development of antioxidant activity packages of foods, and essential oil has abundant phenolic compounds, has both antioxidant and antibacterial activities, and is a substance with great prospect. The essential oil is used as a gas-phase antioxidant, can be diffused to any space in a package without contacting with food, can play a role in antioxidation protection on the surface of the food and the headspace environment in the package, and has high-efficiency antioxidant activity.
However, the release rate of the antioxidant cannot be greatly reduced only by adding the antioxidant into the packaging material, and in order to ensure the sustained release of the antioxidant in a relatively long period of time, more and more researchers at home and abroad begin to develop controlled-release antioxidant activity packages, wherein the liposome technology is favored by more and more researchers at home and abroad due to the characteristics of stability, no toxicity and slow release. The essential oil is extremely easy to volatilize and has special aromatic flavor, the essential oil is wrapped in the liposome form, the essential oil can be isolated from the external environment and slowly released from the liposome, the volatility of the essential oil can be reduced, the influence of the essential oil on the flavor of food can be reduced, the liposome can also protect the main active ingredients of the essential oil, the subcellular size of the liposome can reduce the resistance of the essential oil in the transmission process, and the antioxidant effect of the essential oil can be improved. Meanwhile, the incorporation of the essential oil liposome into the polymer matrix of the packaging film or the coating on the surface of the packaging film to prepare the antioxidant active packaging film is a new development direction.
The external circulation environment is changeable instantly, the internal environmental factors of the package are complex and difficult to detect, at present, most antioxidants in antioxidant activity packages are released immediately after the package preparation is finished, cannot be coordinated with the external environment change and the internal packaging factors, have no excitation mechanism for controlling the release, and cannot realize the intelligent controllable release in the whole circulation use process. The development of a novel intelligent response type controlled-release antioxidant packaging system can effectively realize the organic combination of packaging and food, realize the intelligent control release of antioxidants in the food circulation process according to needs, improve the safety and quality of the food and prolong the shelf life of the food, so that the preparation of the novel intelligent response type antioxidant active packaging film by combining natural antioxidant plant essential oil with a liposome technology and intelligent temperature response has important engineering value.
Disclosure of Invention
The invention provides a temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane and a preparation method thereof.
The technical scheme is that the preparation method of the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane is characterized by comprising the following steps of:
(1) preparation of Temperature Sensitive Polyurethane (TSPU) solution
Firstly, weighing polycaprolactone 4000 (PCL 4000), polyethylene glycol 2000 (PEG 2000) and 4,4 '-diphenylmethane diisocyanate (MDI) and uniformly mixing, wherein the molar ratio of the mixture of the polycaprolactone 4000 and the polyethylene glycol 2000 to the 4, 4' -diphenylmethane diisocyanate is 1 (2 ~ 2.5.5), the molar ratio of the polycaprolactone 4000 to the polyethylene glycol 2000 is 1: 2, and the reaction is carried out at 75 ~ 85 ℃ for 2 ~ 2.5.5 h to obtain a temperature-sensitive polyurethane prepolymer, and adding N, N-Dimethylformamide (DMF) to ensure that the solid content of the system is 45 ~ 55 wt%;
secondly, adding 4,4 '-diphenylmethane diisocyanate and 1, 4' -Butanediol (BDO) to carry out chain extension reaction, controlling the molar ratio of isocyanate (-NCO) to hydroxyl (-OH) in the system to be 1:1, reacting for 2 ~ 2.5.5 h at 75 ~ 85 ℃, and obtaining a transparent viscous temperature-sensitive polyurethane solution with the final solid content of 25 ~ 35 wt%;
(2) preparation of freeze-dried liposome of essential oil
Weighing plant essential oil, soybean lecithin and cholesterol, fully dissolving in an organic solvent, uniformly mixing, wherein the mass ratio of the soybean lecithin to the cholesterol and the mass ratio of the soybean lecithin to the plant essential oil are both 2:1 ~ 10:1, the content of the soybean lecithin in the solution is 15 ~ 35mg/mL, removing the organic solvent by reduced pressure evaporation, adding a hydration solution and a surfactant, carrying out ultrasonic hydration on the solution to form a liposome suspension, carrying out ultrasonic crushing on the liposome suspension system, centrifuging, filtering with a filter membrane, and carrying out freeze drying to obtain an essential oil freeze-dried liposome;
(3) preparation of composite membranes
Adding the freeze-dried liposome of the essential oil into a temperature-sensitive polyurethane solution to prepare a temperature-sensitive polyurethane gas-phase controlled-release antioxidant membrane, wherein the mass ratio of the freeze-dried liposome of the essential oil to the temperature-sensitive polyurethane gas-phase controlled-release antioxidant membrane is 0.5 ~ 2%;
and compounding the temperature-sensitive polyurethane gas-phase controlled-release antioxidant film on the barrier film to prepare the composite film.
Further, in the step (2), the plant essential oil is any one of rosemary essential oil, cinnamon essential oil, clove essential oil, tea tree essential oil and cardamom essential oil or is formed by mixing more than two of the rosemary essential oil, the cinnamon essential oil, the clove essential oil, the tea tree essential oil and the cardamom essential oil.
Further, the hydration solution in the step (2) is phosphate buffer solution prepared according to the standard of Chinese pharmacopoeia 2005 edition, and the pH value is 6.5 ~ 7.4.4.
Further, in the step (2), the surfactant is one or two of polyvinylpyrrolidone (PVP) and Tween 80, the organic solvent is chloroform, the volume concentration of the Tween 80 is 0% ~ 5%, and the concentration of the polyvinylpyrrolidone is 0 ~ 2 mg/mL.
Further, the ultrasonic crushing in the step (2) has the ultrasonic power of 300w, the starting time of 3s, the stopping time of 4s, the time of 15min, the speed of 5000rpm and the centrifugation time of 15 min.
Further, the ultrasonic hydration in the step (2) has ultrasonic power of 250W and ultrasonic time of 30 min.
Further, the conditions of the freeze-drying in the step (2) are that the pre-freezing temperature is set to-80 ℃, the pre-freezing time is set to 6 ~ 10h, and the freeze-drying time is set to 36 ~ 48 h.
Further, in the step (3), the barrier film is formed by compounding any one or more than two of a high-temperature resistant polyester film (PET film), a biaxially oriented polyester film (BOPET film), a polypropylene film (PP film), a polyamide film (PA film) and a polyvinyl chloride film (PVC film).
Further, the compounding method in the step (3) is a coating method or a hot-press bonding method.
A temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane can realize intelligent regulation and control of the release of essential oil in the membrane through intelligent response to the external temperature within a certain temperature range, and can effectively slow down the release rate of the essential oil in the membrane through the controlled-release action of the liposome, prolong the antioxidant action time of the essential oil, achieve the long-acting antioxidant effect and further prolong the quality guarantee period of food; the temperature-sensitive polyurethane gas-phase controlled-release antioxidant film can realize dual controlled-release functions of intelligent temperature response controlled release and liposome controlled release, can effectively realize organic combination of packaging and food, realizes intelligent controlled release of antioxidants as required in the food circulation process, improves the safety and quality of food, and has important academic research value and engineering value.
Drawings
FIG. 1 shows DSC thermal analysis curves of TSPU film, A film, B film and C film in the example of the present invention.
FIG. 2 is an analysis of internal crystallization of TSPU, BOPET, A, B and C films in the examples of the present invention.
FIG. 3 shows the moisture permeability analysis of a TSPU film and a general polyurethane film (PU) in the embodiment of the present invention.
FIG. 4 is a graph showing the release profile of rosemary essential oil from membrane A at different temperatures in the examples of the present invention.
FIG. 5 is a graph showing the release profile of rosemary essential oil from pellicle C at different temperatures in accordance with the present invention.
Detailed Description
The present invention will be described in more detail with reference to examples.
Examples
A temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane is prepared by the following method.
(1) Preparation of Temperature Sensitive Polyurethane (TSPU) solution
Adopting a two-step solution block copolymerization technology to synthesize a temperature-sensitive polyurethane solution: firstly, uniformly mixing a mixture of 0.005 mol of PCL4000 (the Ministry of Camphor wood plastic and space plastic raw material Ministry of Dongguan city) and 0.010 mol of PEG2000 (chemical purity (CP), national medicine group chemical reagent company, Ltd.) with 0.030 mol of MDI in a four-neck flask, reacting at 80 ℃ for 2 h to obtain a TSPU prepolymer, and adding DMF according to the viscosity of a reaction system to ensure that the solid content of the system is 50 wt%; measuring the content of free isocyanate group (-NCO) in the system in the first step by an acetone-di-n-butylamine titration method;
and secondly, adding 0.060 mol of MDI and 0.0750 mol of BDO to carry out chain extension reaction, controlling the molar ratio of-NCO to-OH in the system to be 1:1, stirring by a high-speed digital display type stirrer at 150r/min, reacting for 2 h at 80 ℃, and controlling the solid content of the final system to be 30 wt% to obtain a transparent and viscous TSPU solution.
(2) Preparation of freeze-dried liposome of essential oil
Preparing the essential oil freeze-dried liposome by adopting a thin film ultrasonic dispersion method:
fully dissolving 1.00 g of rosemary essential oil (ChromaDex, USA) and 6.00 g of soybean lecithin (more than or equal to 0.995 Biochemical Reagent (BR), national drug group chemical reagent Co., Ltd.) and 1.00 g of cholesterol in trichloromethane, uniformly mixing, wherein the content of the soybean lecithin is 35mg/mL, transferring to a round-bottom flask, and removing the trichloromethane by reduced pressure evaporation with a rotary evaporator until a uniform and transparent lipid membrane appears;
adding 300 ml of phosphate buffer solution with the pH value of 6.8 to dissolve lipid membranes on the bottle walls, simultaneously adding 0.30 g of PVP (grade: not less than 0.995, national drug group chemical reagents Co., Ltd.) and 9 ml of Tween 80 as surfactants, carrying out ultrasonic hydration (ultrasonic power of 250W and ultrasonic time of 30 min) on the solution to form liposome suspension, carrying out ultrasonic crushing again (ultrasonic power of 300W, starting for 3s, stopping for 4s and time of 15 min) to obtain rosemary essence oil liposome with smaller particle size, removing upper-layer free essential oil and lower-layer precipitate after centrifugation, taking intermediate liquid, carrying out centrifugation at the speed of 5000rpm and time of 15min to remove free essential oil and other impurities in the system, and finally filtering by using a 0.22 mu m microporous filter membrane to remove rosemary essence oil liposome with larger particle size and precipitate or other impurities which are not completely removed after centrifugation, wherein the filtrate is the rosemary essential oil liposome suspension;
freeze-drying the rosemary essence oil liposome suspension to obtain the essential oil freeze-dried liposome, setting the pre-freezing temperature to be-80 ℃ and the pre-freezing time to be 8 hours, and then putting the essential oil freeze-dried liposome into a freeze dryer, wherein the freeze-drying time is set to be 36 hours.
(3) Preparation of composite membranes
Preparing a temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane by adopting a tape casting-compounding method:
adding the freeze-dried liposome into the TSPU solution, and preparing a TSPU film containing the freeze-dried liposome of the essential oil by a solution casting method, wherein the mass ratio of the rosemary essential oil to the TSPU film is 1%; the solution casting method comprises pouring TSPU solution onto polytetrafluoroethylene plate, drying at 60 deg.C for 24 hr to obtain 25 cm × 15 cm × 0.1 mm (length × width × thickness) film, cooling, and sealing for storage;
the TSPU film is used as an inner temperature-sensitive controlled release and liposome controlled release functional layer and coated on BOPET to obtain the temperature-sensitive polyurethane gas-phase controlled release antioxidant composite film A.
Wherein the TSPU film thickness is 0.1 mm, and the BOPET film thickness is 50 μm.
The TSPU film is not very good in barrier property as an inner functional layer, and particularly, the barrier property is reduced when the temperature is increased, so that the external air or oxygen is prevented from permeating into the package through the outer barrier film.
Comparative example
Film B: compared with the preparation method of the composite membrane in the embodiment 1, the difference is that the B membrane is not added with the essential oil freeze-dried liposome or other antioxidants, and the TSPU solution is directly prepared into the membrane and then coated on BOPET.
C, film C: compared with the preparation method of the composite membrane in example 1, the difference is that the essential oil freeze-dried liposome is not formed, but the rosemary essential oil is directly added into the TSPU solution, and the mass ratio of the rosemary essential oil to the TSPU membrane is 1 percent.
Effects of the implementation
1) Phase structure and switch temperature analysis
The testing conditions are nitrogen protection, the testing temperature range is 50 ℃ below zero 50 ~ 200 ℃ at 10 ℃/min, each sample is tested for 2 times, the 1 st test is used for eliminating the thermal history of the TSPU sample, and the switch temperature analysis adopts the 2 nd heating curve.
The results are shown in FIG. 1, where the TSPU film has two separate crystalline melting peaks, 35.26 ℃ and 56.98 ℃. The A film, the B film and the C film respectively have two independent crystallization melting peaks, namely 39.56 ℃, 56.00 ℃, 36.04 ℃, 57.32 ℃, 35.26 ℃ and 57.49 ℃, respectively, correspond to the crystallization melting transition of two soft phase components, namely PEG2000 and PCL4000, and have temperature sensitivity.
2) Analysis of Crystal Properties
A D2 PHASER X-ray diffractometer is adopted, and the test conditions are that the scanning range is 2 theta =5 degrees ~ 40 degrees, the scanning speed is 0.1 s/step, and the scanning step size is 0.02 degrees.
As shown in FIG. 2, the absorption peaks of TSPU film were mainly at 19.6, 21.6, and 23.9 °, the absorption peaks of BOPET film were mainly at 26.9 °, the absorption peaks of A film were mainly at 21.7, 24.0, and 26.0 °, the absorption peaks of B film were mainly at 21.9, 24.2, and 26.0 °, and the absorption peaks of C film were mainly at 21.9, 24.1, and 26.1 °. Since whether 2 θ has a main absorption peak related to the crystallization of its soft segment phase, it can be determined that the soft segment (PCL and PEG) crystals exist in the TSPU film, the A film, the B film and the C film, and the result shows that the addition of liposome or essential oil does not destroy the crystallization form of the soft segment, and the TSPU film still has the temperature response characteristic.
3) TSPU film moisture permeability analysis (temperature response characteristic verification)
The ASTM E-96A standard of the American society for testing and materials was used. The test condition is that equivalent drying agent CaCl is added into 3 identical moisture permeable cups2The cup mouth is covered by a TSPU film, the periphery is sealed tightly by sealing glue to ensure that water vapor can only be transmitted through the TSPU film, and then the moisture permeable cup is placed in a constant temperature and humidity box. The program is set to 25 ℃, 50% RH, 24h, and CaCl in the moisture permeable cup is measured after 24h2The quality of (2) is changed. The above operation was repeated while changing the temperature to 35, 45, 55, 65 ℃. The water vapor transmission capacity (WVT) can be calculated by the following formula: WVT =24 × (W)2-W1) /(t × S), wherein W1In order to permeate water CaCl2An initial mass (g); w2After 24h treatment, the CaCl in the moisture permeable cup is permeated2The mass (g) and t are the test time (h); s is the area (m) of the cup rim of the moisture permeable cup2）。
As a result, as shown in FIG. 3, no abrupt change in the moisture permeability of the PU film occurred; the WVT of the TSPU film has 2 sudden changes around the switching temperature of 35.3 ℃ and 57.0 ℃, and shows 2 temperature response characteristics, and when the temperature is changed from 25 ℃ to 35 ℃, the WVT is 70.49 g/m224h rise to 145.71 g/m224h, the amplification rate is 106.71 percent, and when the temperature is changed from 55 ℃ to 65 ℃, the WVT is from 306.32 g/m224h rise to 578.54 g/m2And 24h, the amplification rate is 88.87%. The result shows that the TSPU film has temperature sensitive characteristic, changes the phase state of the soft section of TSPU through temperature control, controls the size of free volume hole size, can effectively realize the control to TSPU film moisture permeability to realize its intelligent temperature response characteristic, and then can reduce the steam content in the package, reduce the speed otherwise of microorganism, and then restrain the oxidative decomposition of grease, can prevent food from being affected with damp simultaneously, guarantee taste such as fragility, fragrance.
4) Antioxidant Release behavior
Solid phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) was used. Researching the release behavior of rosemary essential oil in temperature-sensitive polyurethane gas-phase controlled-release antioxidant membranes at different temperatures, putting samples of the membrane A and the membrane C (40 mm multiplied by 40 mm) into 15 mL brown sample bottles, equally dividing the samples of the membrane A and the membrane C into 3 parts, respectively carrying out release experiments at 25 ℃, 40 ℃ and 60 ℃, and measuring the release amount of the rosemary essential oil in the membrane A and the membrane C at different temperatures every 3 days. Finally, diffusion coefficient fitting is carried out through Matlab software programming, and fitting curves are shown in fig. 4 and 5. The diffusion coefficients D at 25 ℃, 40 ℃ and 60 ℃ are shown in Table 1.
TABLE 1 diffusion coefficient D of rosemary essential oil in film A and film C at different temperatures
As can be seen from table 1, the diffusion coefficient D of the a film at 25 ~ ℃ and 40 ~ ℃ is 32.63% and 28.24% respectively, the diffusion coefficient D of the C film at 25 ~ ℃ and 40 ~ ℃ is 31.27% and 12.97% respectively, and intelligent response to temperature can be achieved, and the C film to which pure essential oil is added has a higher diffusion coefficient which is about 2.02 ~.32 times that of the a film to which the lyophilized liposome of essential oil is added, and the rosemary essential oil is encapsulated in the form of liposome, so that diffusion of essential oil from the film can be effectively slowed down, thereby prolonging the oxidation resistance time thereof.
Therefore, the temperature-sensitive polyurethane gas-phase controlled-release antioxidant membrane prepared by the invention has good temperature response characteristic in a certain temperature range, can realize intelligent regulation and control of the release of essential oil in the membrane, and meanwhile, the liposome can play a good controlled-release role in the release of the essential oil in the membrane, thereby effectively prolonging the antioxidant action time.
The marked preservation mode of a plurality of common packaged foods and self-produced bulk foods is mostly normal temperature preservation, which generally refers to 20-25 ℃, when the ambient temperature exceeds 25 ℃, especially in the range of 35 ~ 55 ℃, the foods are most easily oxidized by lipid, and the phase transition temperature of the A film of the invention is 35.3 ℃ and 57.0 ℃, which is matched with the temperature range of 35 ~ 55 ℃.
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the above embodiments. It is to be understood that other modifications and variations directly derived or suggested to those skilled in the art without departing from the spirit and scope of the present invention are deemed to be within the scope and spirit of the present invention.
Claims (10)
1. A preparation method of a temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane is characterized by comprising the following steps:
(1) preparation of temperature-sensitive polyurethane solution
Firstly, weighing and uniformly mixing polycaprolactone 4000, polyethylene glycol 2000 and 4,4 '-diphenylmethane diisocyanate, wherein the molar ratio of the mixture of the polycaprolactone 4000 and the polyethylene glycol 2000 to the 4, 4' -diphenylmethane diisocyanate is 1 (2 ~ 2.5.5), the molar ratio of the polycaprolactone 4000 to the polyethylene glycol 2000 is 1: 2, and the polycaprolactone 4000 to the polyethylene glycol 2000 react at 75 ~ 85 ℃ for 2 ~ 2.5.5 hours to obtain a temperature-sensitive polyurethane prepolymer, and adding N, N-dimethylformamide to ensure that the solid content of the system is 45 ~ 55 wt%;
secondly, adding 4,4 '-diphenylmethane diisocyanate and 1, 4' -butanediol for chain extension reaction, controlling the molar ratio of isocyanate groups to hydroxyl groups in the system to be 1:1, reacting at 75 ~ 85 ℃ for 2 ~ 2.5.5 h, and obtaining a transparent viscous temperature-sensitive polyurethane solution, wherein the solid content of the system is 25 ~ 35 wt%;
(2) preparation of freeze-dried liposome of essential oil
Weighing plant essential oil, soybean lecithin and cholesterol, fully dissolving in an organic solvent, uniformly mixing, wherein the mass ratio of the soybean lecithin to the cholesterol and the mass ratio of the soybean lecithin to the plant essential oil are both 2:1 ~ 10:1, the content of the soybean lecithin in the solution is 15 ~ 35mg/mL, removing the organic solvent by reduced pressure evaporation, adding a hydration solution and a surfactant, carrying out ultrasonic hydration on the solution to form a liposome suspension, carrying out ultrasonic crushing on the liposome suspension system, centrifuging, filtering with a filter membrane, and carrying out freeze drying to obtain an essential oil freeze-dried liposome;
(3) preparation of composite membranes
Adding the freeze-dried liposome of the essential oil into a temperature-sensitive polyurethane solution to prepare a temperature-sensitive polyurethane gas-phase controlled-release antioxidant membrane, wherein the mass ratio of the freeze-dried liposome of the essential oil to the temperature-sensitive polyurethane gas-phase controlled-release antioxidant membrane is 0.5 ~ 2%;
and compounding the temperature-sensitive polyurethane gas-phase controlled-release antioxidant film on the barrier film to prepare the composite film.
2. The preparation method of the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane according to claim 1, characterized in that: in the step (2), the plant essential oil is formed by mixing any one or more than two of rosemary essential oil, cinnamon essential oil, clove essential oil, tea tree essential oil and cardamom essential oil.
3. The preparation method of the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane according to claim 1, wherein the hydration solution in the step (2) is a phosphate buffer solution prepared according to the standard of Chinese pharmacopoeia 2005 edition, and the pH value is 6.5 ~ 7.4.4.
4. The preparation method of the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane according to claim 1, wherein the surfactant in the step (2) is one or two of polyvinylpyrrolidone and tween 80, the organic solvent is chloroform, the volume concentration of the tween 80 is 0% ~ 5%, and the concentration of the polyvinylpyrrolidone is 0 ~ 2 mg/mL.
5. The preparation method of the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane according to claim 1, characterized in that: and (3) ultrasonic hydration is carried out at the ultrasonic power of 250W in the step (2) and the ultrasonic time is 30 min.
6. The preparation method of the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane according to claim 1, characterized in that: and (3) in the step (2), the ultrasonic power of the ultrasonic crushing is 300w, the ultrasonic crushing is started for 3s, the ultrasonic crushing is stopped for 4s, the time is 15min, the speed is 5000rpm, and the ultrasonic crushing is centrifuged for 15 min.
7. The preparation method of the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane according to claim 1, wherein the freeze-drying conditions in the step (2) are that the pre-freezing temperature is set to-80 ℃, the pre-freezing time is set to 6 ~ 10h, and the freeze-drying time is set to 36 ~ 48 h.
8. The preparation method of the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane according to claim 1, characterized in that: the barrier film in the step (3) is any one or more than two of a high-temperature resistant polyester film, a biaxially oriented polyester film, a polypropylene film, a polyamide film and a polyvinyl chloride film.
9. The preparation method of the temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane according to claim 1, characterized in that: the compounding method in the step (3) is a coating method or a hot-pressing bonding method.
10. A temperature-sensitive polyurethane gas-phase controlled-release antioxidant composite membrane is characterized in that: which is prepared by the preparation method of any one of claims 1 to 9.
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