Ionic Polymer Oxygen Absorbing Composite Material, Its Preparation Method and Application

Abstract

The present application discloses an ionic polymer oxygen-absorbing composite material, its preparation method and application, relating to the technical field of polymer materials. The preparation method of the ionic polymer oxygen-absorbing composite material comprises the following steps: providing methacrylic acid, dimethylaminoethyl methacrylate, and styrene, mixing and reacting to obtain an ionic polymer; mixing the ionic polymer with a hydrogenated styrene-butadiene block copolymer, white oil, and an oxygen scavenger, and reacting to obtain the ionic polymer oxygen-absorbing composite material. The ionic polymer oxygen-absorbing composite material provided by the present application has excellent oxygen absorption, transparency, and strength.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to an ionic polymer oxygen-absorbing composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Thermoplastic elastomer TPE / TPR is a kind of elastomer that has rubber elasticity at room temperature and can be plastically molded at high temperature. Due to its high elasticity, excellent durability, and easy processing, thermoplastic elastomers are selected as the matrix of oxygen-absorbing gaskets for beer and beverage packaging, such as SBS, SEBS, and SEPS. Nowadays, more and more beer or beverage products need to scan the two-dimensional code printed on the bottle cap through the oxygen-absorbing gasket.

[0003] However, in the related art, due to its linear molecular chain structure, ordinary oxygen-absorbing materials have poor solvent resistance. After being soaked and swollen by beer or beverage for a long time, they will gradually change from transparent to semi-transparent or opaque, affecting the scanning of the bottle cap two-dimensional code. Summary of the Invention

[0004] In view of this, the present application provides an ionic polymer oxygen-absorbing composite material, a preparation method thereof, and an application thereof.

[0005] The preparation method of an ionic polymer oxygen-absorbing composite material according to an embodiment of the present application includes the following steps:

[0006] Provide methacrylic acid, dimethylaminoethyl methacrylate, and styrene, mix and react to obtain an ionic polymer;

[0007] Mix the ionic polymer with a hydrogenated styrene-butadiene block copolymer, white oil, and an oxygen scavenger, and react to obtain an ionic polymer oxygen-absorbing composite material.

[0008] Optionally, in some embodiments of the present application, the molar ratio of methacrylic acid, dimethylaminoethyl methacrylate, and styrene is (0.2 - 0.4)∶(0.2 - 0.4)∶(0.2 - 0.6); and / or

[0009] The preparation method of the ionic polymer further includes adding a solvent; and / or

[0010] The preparation method of the ionic polymer further includes adding a catalyst.

[0011] Optionally, in some embodiments of the present application, the solvent is selected from one or more of ethyl acetate, tetrahydrofuran, chlorobenzene, diethylene glycol monobutyl ether, trimethoxybutanol, triethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol, isopropanol, glycerol, dimethyl sulfoxide, acetone, acetophenone, N,N-dimethylformamide, pyrrole, butyric acid, and cresol; and / or

[0012] The mass ratio of the sum of the masses of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene to the mass of the solvent is 10∶(15 - 25); and / or

[0013] The catalyst is selected from one or more of azobisisobutyronitrile, dicumyl peroxide, and potassium persulfate; and / or

[0014] The mass ratio of the sum of the masses of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene to the mass of the catalyst is (99.7 - 99.9)∶(0.1 - 0.3).

[0015] Optionally, in some embodiments of the present application, the reaction of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene is carried out in an inert atmosphere; and / or

[0016] The reaction of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene is carried out with stirring; the rotation speed of the stirring is 40 rpm - 80 rpm; and / or

[0017] The reaction temperature of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene is 60°C - 80°C, and the time is 6 h - 10 h.

[0018] Optionally, in some embodiments of the present application, the mixing of the ionic polymer, the hydrogenated styrene-butadiene block copolymer, the white oil, and the oxygen scavenger includes:

[0019] Mix the white oil and the oxygen scavenger, and then grind to obtain a premixed material;

[0020] Mix the premixed material with the ionic polymer and the hydrogenated styrene-butadiene block copolymer.

[0021] Optionally, in some embodiments of the present application, the mass ratio of the oxygen scavenger to the white oil is 1∶(4 - 20); and / or

[0022] The grinding further includes adding a grinding medium; the grinding medium includes grinding balls, and the average particle size of the grinding balls is 0.25 mm - 0.85 mm; and / or

[0023] The rotation speed of the grinding is 3000 rpm to 3500 rpm; and / or

[0024] The grinding time is 10 min to 15 min.

[0025] Optionally, in some embodiments of the present application, the oxygen scavenger includes one or more of sodium sulfite, bis(hydroxymethyl) ether, and metal powder; and / or

[0026] The masses of the ionomer, the hydrogenated styrene-butadiene block copolymer, the white oil, and the oxygen scavenger are (25 - 50):(40 - 50):(10 - 30):(1 - 5).

[0027] Optionally, in some embodiments of the present application, the reaction of the ionomer, the hydrogenated styrene-butadiene block copolymer, the white oil, and the oxygen scavenger includes extrusion molding, wherein

[0028] The temperature of the extrusion molding is 180°C to 220°C; and / or

[0029] The rotation speed of the extrusion molding is 200 rpm / min to 500 rpm / min; and / or

[0030] The feeding rotation speed of the extrusion molding is 100 r / min to 200 r / min.

[0031] Correspondingly, an ionomer oxygen-absorbing composite material is further provided in an embodiment of the present application, which is prepared by the preparation method described in any one of the above.

[0032] Correspondingly, a gasket is further provided in an embodiment of the present application. The material of the gasket includes the composite material prepared by the preparation method described in any one of the above, or includes the above composite material.

[0033] The preparation method of the ionomer oxygen-absorbing composite material provided by this application uses methacrylic acid as the anionic unit and dimethylaminoethyl methacrylate as the cationic unit to prepare an amphoteric ionomer through random copolymerization. The side chains of the structural units are large in volume, and the molecular chains cannot be arranged regularly, ensuring its transparency. Styrene is used as a comonomer to improve the compatibility between the ionomer and SEBS, ensuring that the prepared oxygen-absorbing composite material has both excellent transparency and mechanical properties. The composite material is prepared using an ionomer, SEBS, white oil, and an oxygen scavenger as raw materials. Due to the large number of branched structures in the ionomer, and the side chains form a dynamic crosslinked network that can be dissociated by heating and re-crosslinked by cooling through ionic bond interactions. This unique structure endows the ionomer with excellent solvent resistance, elasticity, and tensile strength. Then, the flexibility and mechanical toughness of the oxygen-absorbing composite material are adjusted by blending an appropriate amount of SEBS to meet the sealing requirements of different products. The preparation method provided by this application is simple to operate, the raw materials are easily available, and a composite material with excellent transparency, strength, and toughness can be efficiently prepared. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the embodiments of this application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of this application. For those skilled in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0035] Figure 1 It is a flowchart of the preparation method of an ionomer oxygen-absorbing composite material provided by an embodiment of this application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] The following will clearly and completely describe the technical solutions in the embodiments of this application in conjunction with the drawings in the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, rather than all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of this application. In addition, it should be understood that the specific embodiments described here are only used to illustrate and explain this application, and are not used to limit this application.

[0037] In this application, unless otherwise stated, the orientation terms such as "upper" and "lower" usually refer to the upper and lower in the actual use or working state of the device, specifically the drawing direction in the drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc. are only used as labels and do not impose numerical requirements or establish an order.

[0038] In this application, "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. Wherein A and B can be singular or plural.

[0039] In this application, "at least one" means one or more, and "a plurality" means two or more. "One or several", "at least one (item) below" or similar expressions refer to any combination of these items, including any combination of single items (pieces) or plural items (pieces). For example, "at least one (item) of a, b, or c", or "at least one (item) of a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0040] The various embodiments of this application can exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub - ranges and individual values within that range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub - ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and individual numbers within the range, such as 1, 2, 3, 4, 5, and 6, and this applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0041] The structural formulas and molecular weights of some chemical reagents used in this application are described as follows:

[0042] Methacrylic acid (AA): Molecular weight = 86.09;

[0043] Dimethylaminoethyl methacrylate (DMAEMA): Molecular weight = 157.21;

[0044] Styrene: Molecular weight = 104.15.

[0045] The technical solution of this application is as follows:

[0046] In a first aspect, please refer to Figure 1 , an embodiment of this application provides a method for preparing an ion - polymer oxygen - absorbing composite material, including the following steps:

[0047] S11. Provide methacrylic acid (AA), dimethylaminoethyl methacrylate (DMAEMA), and styrene, mix them, and react to obtain an ionic polymer;

[0048] S12. Mix the ionic polymer, hydrogenated styrene-butadiene block copolymer (SEBS), white oil, and oxygen scavenger, and react to obtain an ionic polymer oxygen-absorbing composite material.

[0049] In the preparation method of the ionic polymer oxygen-absorbing composite material provided by this application, methacrylic acid is used as the anionic unit, and dimethylaminoethyl methacrylate is used as the cationic unit. An amphoteric ionic polymer is prepared by random copolymerization. The side chains of the structural units are large in volume, and the molecular chains cannot be arranged regularly, ensuring its transparency. Styrene is used as the comonomer to improve the compatibility between the ionic polymer and SEBS, ensuring that the prepared oxygen-absorbing composite material has both excellent transparency and mechanical properties; the composite material is prepared using the ionic polymer, SEBS, white oil, and oxygen scavenger as raw materials. Due to the existence of a large number of branched structures in the ionic polymer, and the side chains form a dynamic cross-linked network that can be dissociated by heating and re-cross-linked by cooling through ionic bond interactions. This unique structure endows the ionic polymer with excellent solvent resistance, elasticity, and tensile strength. Then, the flexibility and mechanical toughness of the oxygen-absorbing composite material are adjusted by blending an appropriate amount of SEBS to meet the sealing requirements of different products; the preparation method provided by this application is simple in operation, the raw materials are easy to obtain, and a composite material with excellent transparency, strength, and toughness can be efficiently prepared.

[0050] In the above S11:

[0051] In some embodiments, the molar ratio of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene is (0.2 - 0.4):(0.2 - 0.4):(0.2 - 0.6), for example, it can be 0.2:0.2:0.6, 0.3:0.3:0.4, 0.4:0.4:0.2, etc. Within the range of the above molar ratio, it is beneficial for the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene to fully react to form an ionic polymer.

[0052] In some embodiments, the preparation method of the ionic polymer further includes adding a solvent. In other words, the reaction of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene is carried out in a solution.

[0053] In some embodiments, the mass ratio of the sum of the masses of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene to the mass of the solvent is 10:(15 - 25), for example, it can be 10:18, 10:20, 10:22, or within the range between any two ratios, etc. Within this mass ratio range, it is beneficial for the uniform dissolution and dispersion of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene.

[0054] In some embodiments, the solvent is selected from one or more of ethyl acetate, tetrahydrofuran, chlorobenzene, diethylene glycol monobutyl ether, trimethoxybutanol, triethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol, isopropanol, glycerol, dimethyl sulfoxide, acetone, acetophenone, N,N - dimethylformamide, pyrrole, butyric acid, and cresol.

[0055] In some embodiments, the method for preparing the ionomer further includes adding a catalyst.

[0056] In some embodiments, the mass ratio of the sum of the masses of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene to the mass of the catalyst is (99.7 - 99.9):(0.1 - 0.3), for example, it can be 99.7:0.3, 99.8:0.2, 99.9:0.1, or within the range between any two ratios, etc. Within this mass ratio range, it is beneficial to promote the copolymerization reaction of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene.

[0057] In some embodiments, the catalyst is selected from one or more of azobisisobutyronitrile, dicumyl peroxide, and potassium persulfate.

[0058] In some embodiments, the reaction of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene is carried out in an inert atmosphere.

[0059] Further, the inert gas in the inert atmosphere includes one or more of nitrogen, helium, neon, argon, krypton, and xenon.

[0060] In some embodiments, the reaction of the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene is carried out with stirring.

[0061] Further, the rotation speed of the stirring is 40 rpm - 80 rpm, for example, it can be 45 rpm, 50 rpm, 55 rpm, 60 rpm, 65 rpm, 70 rpm, 75 rpm, or within the range between any two values, etc. At the rotation speed of the stirring, it is beneficial for the methacrylic acid, the dimethylaminoethyl methacrylate, and the styrene to be fully mixed and uniform.

[0062] In some embodiments, the temperature of the reaction of the methacrylic acid, the dimethylaminoethyl methacrylate and the styrene is 60°C to 80°C, for example, it can be 65°C, 70°C, 75°C or a range between any two values, etc.; the time is 6h to 10h, for example, it can be 7h, 8h, 9h or a range between any two values, etc. Thus, under the conditions of the reaction, it is beneficial for the methacrylic acid, the dimethylaminoethyl methacrylate and the styrene to fully react to form an ionic polymer.

[0063] In some embodiments, after the reaction of the methacrylic acid, the dimethylaminoethyl methacrylate and the styrene, it further includes precipitation, suction filtration, washing and drying.

[0064] In some embodiments, the structural formula of the ionic polymer is shown as follows:

[0065] Wherein, 0.2 ≤ x ≤ 0.4, 0.2 ≤ y ≤ 0.4, 0.2 ≤ z ≤ 0.6.

[0066] It should be noted that x, y, and z represent the number of moles.

[0067] In the S12:

[0068] It can be understood that SEBS can be obtained by commercial purchase. Such as G1641HU purchased from Kraton Performance Polymers.

[0069] In some embodiments, the masses of the ionic polymer, the hydrogenated styrene-butadiene block copolymer, the white oil and the oxygen scavenger are (25 - 50) : (40 - 50) : (10 - 30) : (1 - 5), for example, it can be 25 : 50 : 20 : 5, 35 : 45 : 16 : 4, 40 : 40 : 18 : 2, 49 : 40 : 10 : 1, etc. Within the range of the mass ratio, it is beneficial for the ionic polymer, the hydrogenated styrene-butadiene block copolymer, the white oil and the oxygen scavenger to fully react to form an ionic polymer oxygen-absorbing composite material, improving the transparency, strength and toughness of the composite material.

[0070] In some embodiments, the mixing of the ionic polymer, the hydrogenated styrene-butadiene block copolymer, the white oil and the oxygen scavenger includes:

[0071] S121. After mixing the white oil and the oxygen scavenger, grind them to obtain a premixed material;

[0072] S122. Mix the premixed material with the ionic polymer and the hydrogenated styrene-butadiene block copolymer.

[0073] In some embodiments, the oxygen scavenger includes one or more of sodium sulfite, dihydroxymethyl ether, and metal powder.

[0074] In some embodiments, the mass ratio of the oxygen scavenger to the white oil is 1∶(4 - 20), such as 1∶5, 1∶8, 1∶10, 1∶12, 1∶15, 1∶18, or the range between any two ratios. Within the range of the mass ratio, it is beneficial for the oxygen scavenger and the white oil to be fully mixed and promote grinding.

[0075] In some embodiments, the grinding further includes adding a grinding medium.

[0076] Furthermore, the grinding medium includes grinding balls, and the average particle size of the grinding balls is 0.25 mm - 0.85 mm, for example, it can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or the range between any two values.

[0077] In some embodiments, the rotation speed of the grinding is 3000 rpm - 3500 rpm, for example, it can be 3100 rpm, 3200 rpm, 3300 rpm, 3400 rpm, or the range between any two values; the grinding time is 10 min - 15 min, for example, it can be 11 min, 12 min, 13 min, 14 min, or the range between any two ratios. Thus, under the conditions of the grinding, it is beneficial for the oxygen scavenger and the white oil to be fully mixed.

[0078] It can be understood that the grinding can be achieved by using conventional equipment in the art, such as a horizontal bead mill.

[0079] In some embodiments, the reaction of the ionic polymer with the hydrogenated styrene - butadiene block copolymer, the white oil, and the oxygen scavenger includes extrusion molding.

[0080] In some embodiments, the temperature of the extrusion molding is 180°C - 220°C, for example, it can be 190°C, 200°C, 210°C, or the range between any two values; the rotation speed of the extrusion molding is 200 rpm / min - 500 rpm / min, for example, it can be 250 r / min, 300 r / min, 350 r / min, 400 r / min, 450 r / min, or the range between any two values; the feeding rotation speed of the extrusion molding is 100 r / min - 200 r / min, for example, it can be 120 r / min, 140 r / min, 150 r / min, 160 r / min, 180 r / min, or the range between any two values.

[0081] Thus, under the conditions of the above extrusion molding, it is beneficial to the molding and granulation of the ionomer oxygen absorption composite material.

[0082] It can be understood that the above extrusion molding can be realized by using conventional equipment in the art, such as a twin-screw extruder.

[0083] In a second aspect, an embodiment of the present application further provides an ionomer oxygen absorption composite material obtained by the above preparation method.

[0084] In a third aspect, the present application further provides an application of the ionomer oxygen absorption composite material prepared by the above preparation method.

[0085] Specifically, a gasket, the material of the gasket includes the ionomer oxygen absorption composite material prepared by the above preparation method.

[0086] In some embodiments, the gasket can be obtained by extruding the ionomer oxygen absorption composite material with a molding machine.

[0087] Further, the extrusion includes segmented heating, and the temperatures of the segmented heating are 90°C - 95°C, 100°C - 105°C, 105°C - 110°C, 110°C - 115°C, and 115°C - 120°C in sequence.

[0088] The motor speed of the extrusion is 1000 r / min - 1500 r / min, for example, it can be 1100 r / min, 1200 r / min, 1300 r / min, 1400 r / min, or a range between any two values, etc.

[0089] The feeding speed of the extrusion is 80 r / min - 100 r / min, for example, it can be 82 r / min, 85 r / min, 88 r / min, 90 r / min, 92 r / min, 95 r / min, 98 r / min, or a range between any two values, etc.

[0090] A bottle cap, the bottle cap includes a bottle cap body and a gasket located inside the bottle cap body, and the material of the gasket includes the ionomer oxygen absorption composite material prepared by the above preparation method.

[0091] In some embodiments, the material of the bottle cap body can be chromium-plated steel sheet.

[0092] The bottle cap can be used for the packaging of beer, beverages, etc.

[0093] The following specifically describes the present application through specific embodiments. The following embodiments are only partial embodiments of the present application and do not limit the present application.

[0094] Example 1

[0095] This embodiment provides an ion polymer oxygen-absorbing composite material, and its preparation method is as follows:

[0096] Weigh 0.3 mol of methacrylic acid, 0.3 mol of dimethylaminoethyl methacrylate, 0.4 mol of styrene, 200 g of ethyl acetate, and 0.1 g of azobisisobutyronitrile, add them to a 500 mL three-necked flask, seal the three-necked flask, replace the air in the reaction kettle with nitrogen, start stirring, and set the stirring speed to 60 rpm; heat up to 70 °C and keep the temperature constant for 8 h. After the reaction is completed, pour the reaction solution into an excess of n-hexane for precipitation, perform suction filtration, wash with ethanol to remove unreacted monomers, and dry to obtain an ion polymer.

[0097] Add sodium sulfite and white oil to the hopper of the DMQ-07 horizontal bead mill at a mass ratio of 5:20, turn on the power supply, turn on the coolant, and at the same time set the rotation speed to 3000 rpm. Select grinding balls with an average particle size of 0.35 mm and perform cyclic grinding for 10 min to obtain a premixed material.

[0098] Based on the mass percentages of each component, mix 35 parts of the ion polymer, 45 parts of SEBS (G1641 HU, purchased from Kraton Performance Polymers Inc.), and 25 parts of the premixed material (20 parts of white oil and 5 parts of sodium sulfite) evenly, and then use a twin-screw extruder. The extrusion temperature is 200 °C, the extrusion speed is 300 r / min, and the feeding speed is 120 r / min for extrusion molding to obtain an ion polymer oxygen-absorbing composite material.

[0099] Example 2

[0100] This example is basically the same as Example 1, except that in this example, the ion polymer oxygen-absorbing composite material contains 35 parts of the ion polymer, 45 parts of SEBS, and 20 parts of the premixed material (16 parts of white oil and 4 parts of sodium sulfite).

[0101] Example 3

[0102] This example is basically the same as Example 1, except that in this example, the ion polymer oxygen-absorbing composite material contains 40 parts of the ion polymer, 40 parts of SEBS, and 20 parts of the premixed material (18 parts of white oil and 2 parts of sodium sulfite).

[0103] Example 4

[0104] This example is basically the same as Example 1, except that in this example, the ion polymer oxygen-absorbing composite material contains 49 parts of the ion polymer, 40 parts of SEBS, and 11 parts of the premixed material (10 parts of white oil and 1 part of sodium sulfite).

[0105] Comparative Example

[0106] This comparative example is basically the same as Example 3, except that in this comparative example, the ionic polymer is replaced by polypropylene.

[0107] The ionic polymer oxygen-absorbing composites of Examples 1 to 4 and the composites of the comparative example were added to the hopper of a DMS-250K molding machine, pressed into gaskets and adhesively bonded to the inside of the bottle cap body to obtain crown cap products for subsequent transparency and oxygen-absorbing performance tests. The specific processing parameters are as follows: the temperatures of the first to fifth zones of the molding machine are 90°C - 95°C, 100°C - 105°C, 105°C - 110°C, 110°C - 115°C, and 115°C - 120°C respectively; the extrusion motor speed is 1000 r / min, the feeding speed is 80 r / min, the material of the bottle cap is chromium-plated steel sheet SPCC-BA, and the average weight of the gasket is 220 mg.

[0108] The ionic polymer oxygen-absorbing composites of Examples 1 to 4 and the composites of the comparative example were subjected to mechanical property tests, and the test results are shown in Table 1.

[0109] Among them, the mechanical property test was carried out in accordance with standard ASTM D638.

[0110] Table 1

[0111]

[0112] As can be seen from Table 1, the tensile strength of the ionic polymer oxygen-absorbing composites provided in Examples 1 to 4 is much higher than that of the composites in the comparative example.

[0113] The ionic polymer oxygen-absorbing composite of Example 3 and the composite of the comparative example were subjected to transparency performance tests, and the test results are shown in Table 2.

[0114] Among them, the test method for transparency performance includes: after preparing the ionic polymer oxygen-absorbing composite or the composite into the gasket of a crown cap, pressing the crown cap on a beer bottle filled with beer by a capping machine, setting 12 groups of samples for each experiment, then inverting for 30 days, removing the bottle cap, using a mobile phone to scan the QR code on the bottle cap, and recording the scanning results. S1 is the ionic polymer oxygen-absorbing material obtained in Example 3, and S2 is the ordinary oxygen-absorbing material obtained in the comparative example. Among them, Y represents can be scanned, and N represents cannot be scanned.

[0115] Table 2

[0116] Sample 1 Sample 2 <![CDATA[Sample 3 > Sample 4 <![CDATA[Sample 5 > <![CDATA[Sample 6 > <![CDATA[Sample 7 > <![CDATA[Sample 8 > <![CDATA[Sample 9 > <![CDATA[Sample 1 0 > Sample 11 Sample 12 S1 Y Y Y Y Y Y Y Y Y Y Y Y S2 Y Y N N N N N N N N N N

[0117] For the convenience of comparison, the data was sorted, and the data that could not be scanned during the actual test was interspersed. As can be seen from Table 2, the QR code scanning rate of Example 3 was 100%. During the 30-day inversion process, its transparency performance was not significantly affected. The QR codes of 12 groups of samples could all be scanned. Compared with 16.7% of the comparative example, the success rate of QR code scanning was greatly improved. This proves that the transparency performance of the ion polymer oxygen-absorbing composite material of Example 3 is greatly improved compared with that of the composite material of the comparative example, and it can meet the requirements of customers for transparent oxygen-absorbing composite materials.

[0118] The oxygen absorption performance of the ion polymer oxygen-absorbing composite materials of Examples 1 to 4 and the composite materials of the comparative examples was tested, and the test results are shown in Table 3.

[0119] Among them, the test method for oxygen absorption performance includes: using (GEN III 5250i, OxySense, Texas, USA) fluorescence residual oxygen analyzer for tracking and testing. By pasting the oxygen sensing film of the instrument on the inner side of the container lid in advance, pouring 400 mL of deionized water into the container, pressing the sample into a thin sheet with a thickness of 0.2 mm in advance, taking 1 g and putting it into the deionized water in the container, sealing it, and purging the chamber with 99.999% high-purity oxygen for 5 minutes. After the purging is completed, close the lid and the valve. At this time, the container containing the sample to be tested has become an oxygen-rich sealed chamber. Place the fluorescence signal reading pen in the groove for measuring dissolved oxygen, and its test point exactly corresponds to the oxygen sensing film. The fluorescence signal reading pen tracks and measures the change data of the dissolved oxygen content in the deionized aqueous solution in the sealed chamber with time. The measurement of oxygen content by fluorescence method is greatly affected by temperature. To eliminate the test fluctuations caused by temperature, place the equipment and the sealed chamber in a constant temperature and humidity chamber. The test temperature condition is 23 ± 2 °C, and the relative humidity is 50 ± 3%. The detection period is 7 days. Each sample is tested three times on average, and the average value is taken.

[0120] Table 3

[0121]

[0122] As can be seen from Table 3, the oxygen absorption performance of the ion polymer oxygen-absorbing composite materials provided in Examples 1 to 4 is much higher than that of the composite materials in the comparative examples.

[0123] In summary, on the basis of excellent oxygen absorption performance, the ion polymer oxygen-absorbing composite material provided in this application has significantly improved strength and toughness.

[0124] The above has introduced the technical solutions provided by the embodiments of the present application in detail. Specific examples are used in this article to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present application.

Claims

1. A method for preparing an ion polymer oxygen absorbing composite material, characterized in that: The steps include: Providing methacrylic acid, dimethylaminoethyl methacrylate and styrene, mixing and reacting them to obtain an ionomer; The ionomer is mixed with hydrogenated styrene-butadiene block copolymer, white oil and oxygen scavenger to react and obtain an ionomer oxygen absorbing composite material; The molar ratio of the methacrylic acid, the dimethylaminoethyl methacrylate and the styrene is (0.2-0.4):(0.2-0.4):(0.2-0.6).

2. The preparation method according to claim 1, characterized in that The method for preparing the ionic polymer further comprises adding a solvent; and / or The method for preparing the ionic polymer further comprises adding a catalyst.

3. The preparation method according to claim 2, characterized in that: The solvent is selected from one or more of ethyl acetate, tetrahydrofuran, chlorobenzene, diethylene glycol monobutyl ether, trimethoxybutanol, triethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol, isopropanol, glycerol, dimethyl sulfoxide, acetone, acetophenone, N,N-dimethylformamide, pyrrole, butyric acid, and cresol; and / or The mass ratio of the methacrylic acid, the dimethylaminoethyl methacrylate and the styrene to the solvent is 10:(15-25); and / or The catalyst is selected from one or more of azobisisobutyronitrile, dicumyl peroxide, and potassium persulfate; and / or The mass ratio of the methacrylic acid, the dimethylaminoethyl methacrylate and the styrene to the catalyst is (99.7-99.9):(0.1-0.3).

4. The preparation method according to claim 3, characterized in that: The reaction of the methacrylic acid, the dimethylaminoethyl methacrylate and the styrene is carried out in an inert atmosphere; and / or The reaction of the methacrylic acid, the dimethylaminoethyl methacrylate and the styrene is carried out under stirring; the stirring speed is 40 rpm to 80 rpm; and / or The reaction temperature of the methacrylic acid, the dimethylaminoethyl methacrylate and the styrene is 60° C. to 80° C., and the reaction time is 6 h to 10 h.

5. The preparation method according to claim 1, characterized in that: The mixing of the ionomer, the hydrogenated styrene-butadiene block copolymer, the white oil, and the oxygen scavenger comprises: The white oil and the oxygen scavenger are mixed and ground to obtain a premixed material; The premix material is mixed with the ionomer and the hydrogenated styrene-butadiene block copolymer.

6. The preparation method according to claim 5, characterized in that: The mass ratio of the oxygen scavenger to the white oil is 1:(4-20); and / or The grinding further comprises adding grinding media; the grinding media comprises grinding balls, and the average particle size of the grinding balls is 0.25 mm to 0.85 mm; and / or The grinding speed is 3000 rpm to 3500 rpm; and / or The grinding time is 10 min to 15 min.

7. The preparation method according to claim 1, characterized in that: The oxygen scavenger comprises one or more of sodium sulfite and bis(hydroxymethyl) ether; and / or The masses of the ion polymer, the hydrogenated styrene-butadiene block copolymer, the white oil and the oxygen scavenger are (25-50): (40-50): (10-30): (1-5).

8. The preparation method according to claim 1, characterized in that: The reaction of the ionomer with the hydrogenated styrene-butadiene block copolymer, the white oil and the oxygen scavenger comprises extrusion molding, wherein: The extrusion molding temperature is 180°C to 220°C; and / or The extrusion speed is 200 rpm / min to 500 rpm / min; and / or The feeding speed of the extrusion molding is 100r / min~200r / min.

9. An ion polymer oxygen absorbing composite material, characterized in that: The method is prepared according to any one of claims 1 to 8.

10. A sealing gasket, characterized in that: The material of the sealing gasket includes the composite material prepared by the preparation method according to any one of claims 1 to 8, or includes the composite material according to claim 9.

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