CN114749040A - SPEEK/PEG/PVDF gas regulation composite membrane, preparation and application thereof - Google Patents

SPEEK/PEG/PVDF gas regulation composite membrane, preparation and application thereof Download PDF

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CN114749040A
CN114749040A CN202210206509.6A CN202210206509A CN114749040A CN 114749040 A CN114749040 A CN 114749040A CN 202210206509 A CN202210206509 A CN 202210206509A CN 114749040 A CN114749040 A CN 114749040A
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speek
peg
pvdf
composite membrane
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朱良
杨培培
肖凯军
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Guangdong Huakai Mingxin Technology Co ltd
South China University of Technology SCUT
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Guangdong Huakai Mingxin Technology Co ltd
South China University of Technology SCUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B7/148—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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Abstract

The invention belongs to the technical field of membrane materials, and discloses a SPEEK/PEG/PVDF gas regulation composite membrane, and preparation and application thereof. The invention takes low-density polyvinylidene fluoride (PVDF) as a main material, and adds two functions of sulfonated polyether ether ketone (SPEEK) and polyethylene glycol (PEG)And (3) a performance auxiliary material, namely a self-made gas regulation composite membrane. The preparation method of the composite membrane comprises the following steps: stirring and dissolving SPEEK and PEG in DMF, adding PVDF into a blending solution of the SPEEK and the PEG, stirring and dissolving to obtain a membrane casting solution, and preparing the SPEEK/PEG/PVDF gas regulation composite membrane by adopting a solution volatilization method. The invention has simple preparation and easy control of film forming conditions, and the obtained gas separation film has high gas permeability and high CO2/O2Selectivity, obvious inhibition effect on fruit and vegetable respiration, and can be applied to the field of fruit and vegetable storage and preservation.

Description

SPEEK/PEG/PVDF gas regulation composite membrane, preparation and application thereof
Technical Field
The invention belongs to the technical field of membrane materials, and particularly relates to a SPEEK/PEG/PVDF gas regulation composite membrane, and preparation and application thereof.
Background
The fruit and vegetable agricultural products have strong production seasonality, high water content and vigorous metabolism, and are easy to decay until losing commodity value. Due to the relative lack of the storage, transportation and preservation technical knowledge in China, the lagged storage, transportation and storage facilities, the commercialization treatment technology and the like, the loss of the picked fruits and vegetables is up to 20-30 percent, which is not only the waste of food resources, but also a key factor influencing the fluctuation of market prices. Therefore, the research on the technology of effectively improving the storage and preservation period of fruits and vegetables and maintaining the nutritive value of the fruits and vegetables is urgent.
In order to reduce the problems of spoilage of fruits and vegetables in the circulation link, various food preservation technologies are adopted at home and abroad, and at present, a physical method, a chemical method and a biological method are the most main means. Physical methods include modified atmosphere, irradiation, low temperature refrigeration, etc.; the chemical method comprises adding antistaling agent and disinfecting cleaning agent; the biological method mainly uses natural extracts for fresh keeping. Wherein, the irradiation and low-temperature refrigeration have high requirements on mechanical equipment, complex operation, large energy consumption, easy damage to fruits and vegetables by freezing and the like; harmful residues possibly exist in fruits and vegetables treated by the chemical preservative, which cause harm to human health, and more people abandon the method; the modified atmosphere preservation technology is simple to operate, high in safety, good in preservation effect and low in cost, can be used in combination with other preservation technologies such as low-temperature preservation, chemical preservation and the like, overcomes the defects of high cost, complex operation, environmental pollution and the like of the traditional preservation means, and becomes an important high and new technology for the research of the fruit and vegetable preservation technology in the 21 st century.
The membrane material is the core of the air-conditioned fresh-keeping technology, and common foodAlthough the product packaging material PVDF (polyvinylidene fluoride) has the defects of strong hydrophobicity, high oxygen permeability and the like, the product packaging material PVDF is widely used for the fresh-keeping of fruits and vegetables due to low price. SPEEK (sulfonated polyether ether ketone) on CO2Has better selectivity and permeability, which makes it a hot spot for preparing the modified atmosphere membrane. Chinese patent application 'CN 106633132B' discloses preparation and application of a SPEEK/PVDF gas conditioning composite membrane, but the hydrophilicity and the gas separation coefficient are not high. Therefore, high CO was designed2And O2Separation ratio, can continuously adjust CO in the package2、O2The gas concentration of the film is kept in the atmosphere range suitable for storing the fruits and the vegetables, so that the modified atmosphere film for realizing the long-term fresh keeping of the fruits and the vegetables has wide market prospect.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a preparation method of a SPEEK/PEG/PVDF gas conditioning composite membrane.
The invention also aims to provide the SPEEK/PEG/PVDF gas conditioning composite membrane prepared by the method.
The invention further aims to provide the application of the SPEEK/PEG/PVDF gas regulation composite membrane in gas separation or fruit and vegetable storage.
The purpose of the invention is realized by the following scheme:
a preparation method of a SPEEK/PEG/PVDF gas regulation composite membrane comprises the following steps:
(1) adding Polyetheretherketone (PEEK) to a container, and then adding concentrated H2SO4Heating and stirring until PEEK is completely dissolved to obtain a brown yellow solution, slowly pouring the brown yellow solution into an ice water mixture to separate out a white filiform product, and washing and drying the filiform product to obtain sulfonated polyether ether ketone (SPEEK);
(2) dissolving sulfonated polyether ether ketone (SPEEK), polyethylene glycol (PEG) and polyvinylidene fluoride (PVDF) in an organic solvent together, obtaining a membrane casting solution after complete dissolution, standing, casting the membrane casting solution on a flat plate to form a membrane, drying, and uncovering the membrane to obtain the SPEEK/PEG/PVDF gas regulation composite membrane.
Step (ii) of(1) The consumption of PEEK meets the following requirements: 200-250mL concentrated H is correspondingly added into each 10g of PEEK2SO4(ii) a The dissolution is that the solution is stirred to dissolve at the temperature of 60-70 ℃; said rich H2SO4The concentration is 98 percent;
the washing in the step (1) refers to repeatedly washing the product with water until the pH value is neutral; the drying refers to drying at 80-85 ℃ for 10-12h, preferably drying at 80 ℃ for 12 h;
the molecular weight of the PEG in the step (2) is 2000, 4000, 6000 or 8000; the mass ratio of SPEEK, PEG and PVDF is (10-2): (2-10): 94; the total mass concentration of SPEEK, PEG and PVDF in the membrane casting solution is 12-15%;
the solvent in the step (2) is one of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO), and is preferably DMF;
dissolving the sulfonated polyether ether ketone (SPEEK), the polyethylene glycol (PEG) and the polyvinylidene fluoride (PVDF) in the solvent in the step (2) by stirring at 60-65 ℃;
the standing time in the step (2) is 20-24h, preferably 24 h;
the flat plate in the step (2) is a glass flat plate, and before the flat plate is used, the flat plate is firstly cleaned by using a detergent, then is washed by using ultrapure water and then is dried, and finally is wiped by using test paper wetted by DMF for later use;
the drying in the step (2) is drying for 1-2 hours at 65-75 ℃;
the membrane uncovering in the step (2) is to immerse the membrane in water for membrane uncovering, and the thickness of the obtained SPEEK/PEG/PVDF gas regulation composite membrane is 16-32 mu m;
the above steps are all carried out at room temperature, the temperatures of which are not explicitly indicated.
A SPEEK/PEG/PVDF gas conditioning composite membrane prepared by the method.
The SPEEK/PEG/PVDF gas regulation composite membrane is applied to gas separation or controlled atmosphere preservation of fruits and vegetables.
The mechanism of the invention is as follows:
with sulfonated polyether ether ketone (SPE)EK) side chain grafted polyoxyethylene preparation method of comb polymer for increasing content of poly-oxy group and adjusting distribution of ether oxygen group to improve CO2The separation performance of (2); after SPEEK and PEG are completely dissolved in DMF, PVDF as a main material is added into a mixed solution of the SPEEK and the PEG, and the SPEEK/PEG/PVDF gas regulation composite membrane is prepared by a solution volatilization method. According to the separation characteristic of the obtained modified atmosphere film, the selective breathable film suitable for modified atmosphere preservation of fruits and vegetables is prepared.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) compared with the common PVDF membrane, the gas separation membrane prepared by the invention has the advantages of high CO separation efficiency2The air permeability is improved by 207 to 226 percent; to CO2/O2The selectivity of (A) is increased by 1.6-4.3 times. Compared with the SPEEK/PVDF gas-regulating membrane, the SPEEK/PEG/PVDF gas-regulating composite membrane prepared by the invention reduces the addition of SPEEK and enhances the fresh-keeping effect.
(2) The SPEEK/PEG/PVDF gas regulation composite membrane prepared by the invention can spontaneously improve CO in a storage environment2Concentration, lowering of O2The concentration of the fruit extract can delay the occurrence of fruit breathing jump and prolong the storable time of the fruits and vegetables.
(3) The SPEEK/PEG/PVDF gas regulation composite membrane prepared by the invention has the thickness of 16-32 μm, and the fresh-keeping period of fruits and vegetables (millennium cherry tomatoes) with high respiratory strength can be prolonged to more than 2 times by using the composite membrane to keep the fruits and vegetables fresh. Compared with the traditional PVDF fresh-keeping material, the SPEEK/PEG/PVDF gas regulation composite membrane has a good inhibition effect on the respiration of fruits and vegetables (millennium cherry tomatoes) with high respiration intensity, can prolong the fresh-keeping period to more than 60 days, and has a good fresh-keeping effect.
Drawings
FIG. 1 is a surface SEM photograph of a SPEEK/PEG/PVDF gas conditioning composite membrane obtained in example 2;
FIG. 2 is a sectional SEM photograph of the SPEEK/PEG/PVDF gas conditioning composite membrane obtained in example 2;
FIG. 3 is an appearance diagram of cherry tomatoes under different packaging conditions;
FIG. 4 shows the CO of cherry tomato under different packaging conditions2A change in content;
FIG. 5 shows cherry tomato O under different packaging conditions2A change in content;
FIG. 6 shows the weight loss of cherry tomatoes under different packaging conditions;
FIG. 7 is a graph showing the change in the rotting rate of cherry tomatoes under different packaging conditions;
FIG. 8 is a graph showing the variation of the hardness of cherry tomatoes under different packaging conditions;
FIG. 9 is a graph of the relative conductivity of cherry tomatoes under different packaging conditions;
FIG. 10 shows the variation of soluble solids of cherry tomatoes under different packaging conditions;
FIG. 11 is a graph comparing the change in vitamin C content of cherry tomatoes under different packaging conditions.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The reagents used in the examples are commercially available without specific reference.
Example 1
(1) 10g of white powder of Polyetheretherketone (PEEK) with the molecular weight of 10000 is put into a 500mL flask, and 200mL of 98% concentrated H is slowly poured into the flask2SO4And stirring for 7 hours at 65 ℃ and 300r/min until PEEK is completely dissolved to obtain a brown yellow solution. Slowly pouring the obtained brown yellow solution into an ice water mixture to separate out a white filiform product, washing the filiform product for multiple times by deionized water until the pH value is neutral, and drying at 80 ℃ for 12h to obtain sulfonated polyether ether ketone (SPEEK), wherein the yield is 12.8g, and the sulfonation Degree (DS) is 64.7%.
(2) Accurately weighing 1.08g of SPEEK and 0.36g of PEG solid with the molecular weight of 6000, putting the SPEEK and the PEG solid into a 150mL beaker, slowly adding 93mL of DMF, stirring at 65 ℃ and 500r/min until the DMF is completely dissolved, adding 11.28g of PVDF with the molecular weight of 100 ten thousand for dissolving to obtain a homogeneous membrane casting solution, and standing at room temperature for 24h to prepare the membrane. Pouring the membrane casting solution on a glass plate, adjusting a membrane scraping knife to 50 mu m thickness, scraping the membrane by using a flat-plate membrane forming method, drying at 65 ℃ for 1.5h, taking out, cooling, immersing in deionized water, uncovering the membrane, and airing to obtain the SPEEK/PEG/PVDF gas regulation composite membrane. The thickness of the obtained SPEEK/PEG/PVDF gas conditioning composite membrane is 23 μm.
Example 2
(1) 10g of white powder of Polyetheretherketone (PEEK) with the molecular weight of 10000 is put into a 500mL flask, and 200mL of 98% concentrated H is slowly poured into the flask2SO4And stirring for 7 hours at 65 ℃ and 300r/min until PEEK is completely dissolved to obtain a brown yellow solution. Slowly pouring the obtained brown yellow solution into an ice water mixture to separate out a white filamentous product, washing the filamentous product for multiple times by deionized water until the pH value is neutral, and drying at 80 ℃ for 12h to obtain sulfonated polyether ether ketone (SPEEK), wherein the yield is 12.8g, and the sulfonation Degree (DS) is 64.7%.
(2) Accurately weighing 0.72g SPEEK and 0.72g PEG solid with molecular weight of 6000, putting into a 150mL beaker, slowly adding 93mL DMF, stirring at 65 ℃ and 500r/min until the DMF is completely dissolved, adding 11.28g PVDF with molecular weight of 100 ten thousand for dissolving to obtain a homogeneous membrane casting solution, standing at room temperature for 24h, and preparing the membrane. Pouring the membrane casting solution on a glass plate, adjusting a membrane scraping knife to 50 mu m thickness, scraping the membrane by using a flat-plate membrane forming method, drying at 65 ℃ for 1.5h, taking out, cooling, immersing in deionized water, uncovering the membrane, and airing to obtain the SPEEK/PEG/PVDF gas regulation composite membrane. The thickness of the obtained SPEEK/PEG/PVDF gas conditioning composite membrane is 22 μm.
The SPEEK/PEG/PVDF gas conditioning composite membrane obtained in example 2 is pretreated by a scanning electron microscope, and is sent to an analysis test center to be subjected to the scanning electron microscope, so that a surface electron microscope scanning image and a section electron microscope scanning image are obtained and are respectively shown in fig. 1 and fig. 2. As observed in the graphs of FIG. 1 and FIG. 2, the SPEEK/PEG/PVDF composite membrane has a smooth and flat surface, and the electron micrograph of the cross section shows a pore structure. It can be proved that micron-level holes exist inside the SPEEK/PEG/PVDF composite membrane, so that gas molecules with different sizes can freely permeate the composite membrane, and the modified atmosphere effect on fruits and vegetables is realized.
Example 3
(1) Taking 10g white powder of Polyetheretherketone (PEEK) with molecular weight of 10000, and placingInto a 500mL flask, 200mL of 98% concentrated H was slowly poured2SO4And stirring for 7 hours at 65 ℃ and 300r/min until PEEK is completely dissolved to obtain a brown yellow solution. Slowly pouring the obtained brown yellow solution into an ice water mixture to separate out a white filiform product, washing the filiform product for multiple times by deionized water until the pH value is neutral, and drying at 80 ℃ for 12h to obtain sulfonated polyether ether ketone (SPEEK), wherein the yield is 12.8g, and the sulfonation Degree (DS) is 64.7%.
(2) Accurately weighing 0.36g SPEEK and 1.08g PEG solid with molecular weight of 6000, putting into a 150mL beaker, slowly adding 93mL DMF, stirring at 65 ℃ and 500r/min until completely dissolving, adding 11.28g PVDF with molecular weight of 100 ten thousand to obtain a homogeneous membrane casting solution, standing at room temperature for 24h, and preparing the membrane. Pouring the membrane casting solution on a glass plate, adjusting a membrane scraping knife to 50 mu m thickness, scraping the membrane by using a flat-plate membrane forming method, drying at 65 ℃ for 1.5h, taking out, cooling, immersing in deionized water, uncovering the membrane, and airing to obtain the SPEEK/PEG/PVDF gas regulation composite membrane. The thickness of the obtained SPEEK/PEG/PVDF gas conditioning composite membrane is 22 μm.
Comparative example
1.44g of SPEEK with 64.7 percent sulfonation Degree (DS) and 11.28g of PVDF with 100 ten thousand molecular weight are accurately weighed and placed into a 150mL beaker, 93mL of DMF is slowly added, the mixture is stirred at 65 ℃ and 500r/min until the DMF is completely dissolved to obtain a homogeneous membrane casting solution, and the homogeneous membrane casting solution is stood at room temperature for 24 hours to prepare the membrane. Pouring the membrane casting solution on a glass plate, adjusting a membrane scraping knife to 50 mu m thickness, scraping the membrane by using a flat membrane forming method, drying at 65 ℃ for 1.5h, taking out, cooling, immersing in deionized water, uncovering the membrane, and airing to obtain the SPEEK/PVDF gas regulation composite membrane. The thickness of the obtained SPEEK/PVDF gas conditioning composite membrane is 22 μm.
Self-made PVDF membrane
Accurately weighing 12.72g of PVDF with the molecular weight of 100 ten thousand, putting the PVDF into a 150mL beaker, slowly adding 93mL of DMF, stirring at 65 ℃ and 500r/min until the PVDF is completely dissolved to obtain a homogeneous membrane casting solution, and standing at room temperature for 24h to prepare the membrane. Pouring the casting film liquid on a glass plate, adjusting a film scraping knife to 50 mu m thickness, scraping the film by a flat film forming method, drying at 65 ℃ for 1.5h, taking out, cooling, immersing in deionized water, uncovering the film, and drying to obtain the PVDF film. The thickness of the PVDF film obtained was 23 μm.
Application examples
The gas regulating composite membrane obtained in example 2 is applied to the preservation of fruits and vegetables (millennium cherry tomatoes) with high respiratory strength: the selected packaged millennium cherry tomatoes are consistent in maturity, size and color and are fresh and complete, the millennium cherry tomatoes are subjected to pretreatment such as disinfection, cleaning and draining, precooled to 5 ℃, the net weight of each box of the millennium cherry tomatoes is controlled to be about 240g, a semi-automatic modified atmosphere packaging machine is adopted, the SPEEK/PEG/PVDF modified atmosphere composite film prepared in the embodiment 2, the SPEEK/PVDF gas regulation composite film prepared in the comparative example and a self-made PVDF film are respectively used for packaging the cherry tomatoes, a blank group (without package) is arranged for comparison, the cherry tomatoes are placed in a constant temperature and constant humidity box with the temperature of 5 ℃ and the RH of 85 percent and sampled once at 6d, the influence of the preservative films on the aspects such as the sensory quality, the gas concentration and the physical and chemical indexes of the millennium cherry tomatoes is recorded, and the preservation effect is evaluated.
TABLE 1 test results of air permeability of PVDF membrane, SPEEK/PEG/PVDF gas control composite membrane, and comparative SPEEK/PVDF gas control composite membrane obtained in examples 1 to 3
Figure BDA0003529384670000071
As can be seen from the data in Table 1, compared with the PVDF membrane and the comparative example, the SPEEK/PEG/PVDF gas conditioning composite membrane of the 3 examples has a certain improvement in the air permeability, and the SPEEK/PEG/PVDF gas conditioning composite membrane of the example 2 is used for CO2And O2The separation coefficient of the porous membrane reaches up to 6.9, is obviously higher than that of the SPEEK/PVDF membrane obtained in the comparative example, and can reduce O in the environment by utilizing the respiratory metabolism of fruits and vegetables when being used for preserving the fruits and vegetables2Increasing the concentration of CO2The concentration can better maintain the dynamic balance between the breath of the fruits and vegetables and the air permeability of the film bag during storage.
The change in appearance of cherry tomatoes under different packaging conditions in example 2 is shown in fig. 3; CO 22The content change is shown in FIG. 4, O2The content change is shown in FIG. 5, the weight loss rate change is shown in FIG. 6, the decay rate change is shown in FIG. 7, the hardness change is shown in FIG. 8, and the hardness change is relative to the content changeThe change in conductivity is shown in fig. 9, the change in soluble solids is shown in fig. 10, and the change in vitamin C content is shown in fig. 11.
As shown in FIG. 3, the peel of blank group and PVDF film treated cherry tomato begins to shrink when stored for 12 d; the cherry tomatoes in the comparative examples also began to mold when stored for 24 d; when the cherry tomatoes are stored for 30 days, the cherry tomatoes in the embodiment 2 are still full in fruit grains and bright in color, so that the fresh appearance quality of the cherry tomatoes is effectively kept; FIGS. 4-5 show that the SPEEK/PEG/PVDF gas conditioning composite membrane can spontaneously improve CO in a storage environment2Concentration, lowering of O2Concentration, thereby delaying the occurrence of cherry tomato breathing jump; from the figures 6 to 11, the SPEEK/PEG/PVDF composite membrane effectively slows down the reduction of the hardness of cherry tomatoes during storage, slows down the increase of the weight loss rate and the decay rate, slows down the increase of the permeability of cytoplasmic membranes, and effectively maintains the soluble solid content and the VC content of the cherry tomatoes. The results of the graphs in fig. 3-11 show that the SPEEK/PEG/PVDF gas component regulating film prepared by the invention has excellent gas regulating capability and good fresh-keeping effect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a SPEEK/PEG/PVDF gas regulation composite membrane is characterized by comprising the following steps:
(1) adding polyetheretherketone to a vessel and then adding concentrated H2SO4Heating and stirring until the polyether-ether-ketone is completely dissolved to obtain a brown yellow solution, slowly pouring the brown yellow solution into an ice water mixture to separate out a white filiform product, and washing and drying the filiform product to obtain sulfonated polyether-ether-ketone;
(2) dissolving sulfonated polyether ether ketone, polyethylene glycol and polyvinylidene fluoride in an organic solvent, completely dissolving to obtain a membrane casting solution, standing, casting the membrane casting solution on a flat plate to form a membrane, drying, and uncovering the membrane to obtain the SPEEK/PEG/PVDF gas regulation composite membrane.
2. The method for preparing a SPEEK/PEG/PVDF gas conditioning composite membrane according to claim 1, wherein: the dosage of the polyether-ether-ketone in the step (1) meets the following requirements: 200-250mL of concentrated H is correspondingly added into each 10g of polyetheretherketone2SO4(ii) a Said rich H2SO4The concentration was 98%.
3. The method for preparing a SPEEK/PEG/PVDF gas conditioning composite membrane according to claim 1, wherein: the washing in the step (1) refers to repeatedly washing the product with water until the pH value is neutral; the drying refers to drying at 80-85 ℃ for 10-12 h.
4. The method of preparing a SPEEK/PEG/PVDF gas regulating composite membrane according to claim 1, wherein: the molecular weight of the PEG in the step (2) is 2000, 4000, 6000 or 8000; the mass ratio of SPEEK, PEG and PVDF is (10-2): (2-10): 94.
5. the method of preparing a SPEEK/PEG/PVDF gas regulating composite membrane according to claim 1, wherein: the total mass concentration of SPEEK, PEG and PVDF in the membrane casting solution in the step (2) is 12-15%.
6. The method of preparing a SPEEK/PEG/PVDF gas regulating composite membrane according to claim 1, wherein: the solvent in the step (2) is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, and is preferably N, N-dimethylformamide; dissolving the sulfonated polyether ether ketone, the polyethylene glycol and the polyvinylidene fluoride in the solvent in the step (2) means stirring and dissolving at 60-65 ℃.
7. The method of preparing a SPEEK/PEG/PVDF gas regulating composite membrane according to claim 1, wherein: the standing time in the step (2) is 20-24h, preferably 24 h; the drying is drying for 1-2 hours at 65-75 ℃.
8. The method according to claim 1, wherein the stripping is performed by immersing in water, and the SPEEK/PEG/PVDF gas control composite membrane has a thickness of 16-32 μm.
9. A SPEEK/PEG/PVDF gas conditioning composite membrane prepared according to the method of any one of claims 1-8.
10. The use of a SPEEK/PEG/PVDF gas regulating composite membrane according to claim 9 in gas separation or modified atmosphere preservation of fruits and vegetables.
CN202210206509.6A 2022-03-03 2022-03-03 SPEEK/PEG/PVDF gas regulation composite membrane, preparation and application thereof Pending CN114749040A (en)

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