Composite film for manufacturing a container bag and a manufacturing process thereof

Abstract

The application relates to the technical field of container liquid bag material research and development, and discloses a composite film for manufacturing a container liquid bag and a preparation process, in particular to the following: based on a Friedel-Crafts alkylation reaction mechanism, a phenyl-POSS functionalized polyethylene and a phenyl-POSS functionalized polypropylene are grafted on the surface of an alkenyl functionalized sheet spacing stable montmorillonite to prepare an organic-inorganic hybrid high-strength filler for modifying a polyolefin base, and through a 11-layer co-extrusion blow molding process, a composite film is prepared; the film product meets the technical requirements stipulated in the TB / T 2689.4-2018 "Railway Freight Containerization Transportation Part 4: Disposable Container Liquid Container Bag" standard and can be used as the inner bag material of the disposable container liquid bag.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of container liquid bag material research and development, in particular to a composite film for manufacturing a container liquid bag and a preparation process. BACKGROUND

[0002] A container liquid bag is a flexible container for storing and transporting non-hazardous, atmospheric liquid chemicals or food, and a disposable liquid bag can not only avoid cross-contamination of materials, but also reduce the cleaning cost of the liquid bag.

[0003] Currently, the product structure of a disposable container liquid bag is usually one outer bag (made of polypropylene woven cloth) and three or more inner bags (made of single-layer or multi-layer co-extruded polyethylene film), which has a low-cost advantage, but also has the defect of insufficient strength, especially in the transportation process, it is difficult to withstand the liquid shock force caused by the violent shaking of the internal liquid, and it is also easy to be scratched or torn in the loading and unloading process, thereby causing the risk of leakage of the packaged product.

[0004] In the prior art, there have been reports of using montmorillonite as a filler to enhance the mechanical strength of the polyethylene inner bag. Montmorillonite is widely available and inexpensive, and can significantly improve the rigidity, strength, barrier properties, etc. of polyethylene at a low addition amount. SUMMARY

[0005] Based on the Friedel-Crafts alkylation reaction mechanism, the present application grafts phenyl-POSS functionalized polyethylene and phenyl-POSS functionalized polypropylene onto the surface of an alkenyl functionalized interlayer spacing stable montmorillonite to prepare an organic-inorganic hybrid high-strength filler for modifying a polyolefin matrix, and through an eleven-layer co-extrusion blow molding process, a composite film is prepared. The film product meets the technical requirements specified in TB / T 2689.4-2018 "Railway Freight Containerization Transportation Part 4: Disposable Container Liquid Set Bag" standard, and can be used as an inner bag material for a disposable container liquid bag.

[0006] The composite film for manufacturing a container liquid bag has a product structure of: LDPE layer / TIE layer / PP layer / TIE layer / PP-PE functional layer / TIE layer / PP-PE functional layer / TIE layer / PP layer / TIE layer / m-LLDPE layer.

[0007] The formula of the LDPE layer is 100wt% low-density polyethylene resin, and the amount is 5-15 parts by weight.

[0008] The formula of the TIE layer is 100wt% maleic anhydride grafted polyethylene resin, and the amount is 1-5 parts by weight.

[0009] The formula of the PP layer is 100wt% polypropylene resin, and the amount is 5-15 parts by weight.

[0010] The formula of the PP-PE functional layer is 30-50wt% low-density polyethylene resin and 50-70wt% organic-inorganic hybrid high-strength filler, and the amount is 15-25 parts by weight;

[0011] The formula of the organic-inorganic hybrid high-strength filler is: 20-30wt% phenyl-POSS functionalized polyethylene, 20-30wt% phenyl-POSS functionalized polypropylene, and 40-60wt% alkenyl functionalized interlayer spacing stable montmorillonite; wherein the phenyl-POSS functionalized polyethylene is prepared by grafting monoalkenyl phenyl-POSS onto the polyethylene main chain through free radical addition reaction; the phenyl-POSS functionalized polypropylene is prepared by grafting monoalkenyl phenyl-POSS onto the polypropylene main chain through free radical addition reaction; and the alkenyl functionalized interlayer spacing stable montmorillonite is prepared by intercalating modification of sodium-based montmorillonite with alkenylated gemini quaternary ammonium salt through ion exchange reaction;

[0012] The formula of the m-LLDPE layer is 100wt% metallocene polyethylene resin, and the amount is 5-15 parts by weight.

[0013] Preferably, the thickness of the composite film is 130-180μm.

[0014] Preferably, the mass ratio of the alkenylated gemini quaternary ammonium salt to the sodium-based montmorillonite in the alkenyl functionalized interlayer spacing stable montmorillonite is 1:(3-8).

[0015] Preferably, the flake diameter of the sodium-based montmorillonite is 3-8μm, and the thickness is 5-15nm.

[0016] Preferably, the mass ratio of the monoalkenyl phenyl-POSS to the polyethylene in the phenyl-POSS functionalized polyethylene is 1:(8-10);

[0017] Preferably, the mass ratio of the monoalkenyl phenyl-POSS to the polypropylene in the phenyl-POSS functionalized polypropylene is 1:(8-10).

[0018] The preparation process of the composite film for manufacturing the container liquid bag comprises the following steps:

[0019] Step one: synthesizing monoalkenyl phenyl-POSS, and sequentially functionalizing polyethylene and polypropylene with monoalkenyl phenyl-POSS to sequentially prepare phenyl-POSS functionalized polyethylene and phenyl-POSS functionalized polypropylene;

[0020] synthesizing alkenylated gemini quaternary ammonium salt, and functionalizing sodium-based montmorillonite with the alkenylated gemini quaternary ammonium salt to prepare alkenyl functionalized interlayer spacing stable montmorillonite;

[0021] Under the action of Lewis acid, Friedel-Crafts alkylation reaction occurs between the phenyl functional groups in the phenyl-POSS functionalized polyethylene and polypropylene and the alkenyl functional groups on the surface of alkenyl functionalized interlamellar spacing stable montmorillonite, and the polyethylene and polypropylene are grafted on the surface of the montmorillonite to prepare the organic-inorganic hybrid high-strength filler;

[0022] Step two: according to the formula of the composite film, the raw materials of each layer are respectively put into the hoppers of the eleven screw extruders of the eleven-layer co-extrusion film blowing machine set, the molten resins are converged at the die head through a flow divider, and the composite film for manufacturing the container liquid bag is prepared through extrusion blowing and traction, cooling and winding.

[0023] Preferably, the preparation method of the alkenyl Gemini quaternary ammonium salt is as follows:

[0024] The amine-alkene addition reaction occurs between the amino functional groups of 3-amino-1-propanol and the alkenyl functional groups of methacryloyloxyethyl trimethyl ammonium chloride, and the molar ratio of 3-amino-1-propanol to methacryloyloxyethyl trimethyl ammonium chloride is controlled to be 1:2.05-2.09, to generate a hydroxyl ammonium chloride monomer;

[0025] The nucleophilic substitution reaction occurs between the hydroxyl functional groups of the hydroxyl ammonium chloride monomer and the acyl chloride functional groups of 10-undecenoyl chloride, and the molar ratio of the hydroxyl ammonium chloride monomer to 10-undecenoyl chloride is controlled to be 1:1.01-1.05, to generate the alkenyl Gemini quaternary ammonium salt.

[0026] Preferably, the preparation method of the monoalkenyl phenyl-POSS is as follows:

[0027] Under the action of Lewis acid, Friedel-Crafts alkylation reaction occurs between the alkenyl functional groups of 10-undecenol and the phenyl functional groups of octaphenyl-POSS, and the molar ratio of octaphenyl-POSS to 10-undecenol is controlled to be 1:0.91-0.95, to generate the monohydroxy phenyl-POSS;

[0028] Under the action of a sulfate, the hydroxyl functional groups of the monohydroxy phenyl-POSS undergo dehydration elimination reaction to generate the monoalkenyl phenyl-POSS.

[0029] Preferably, the Lewis acid is one of aluminum chloride, iron trichloride, tin tetrachloride, and zinc dichloride.

[0030] Preferably, the sulfate is one of aluminum sulfate, zirconium sulfate, and potassium bisulfate.

[0031] Beneficial effects

[0032] The application is based on a molecular design mechanism, and an alkenyl gemini quaternary ammonium salt is prepared by first subjecting 3-amino-1-propanol to an amine-ene addition reaction with methacryloyloxyethyl trimethyl ammonium chloride, and then subjecting the product to a nucleophilic substitution reaction with 10-undecenoyl chloride; the alkenyl gemini quaternary ammonium salt is used as an intercalation agent to perform an intercalation modification treatment on sodium-based montmorillonite through an ion exchange reaction, so as to obtain alkenyl functionalized montmorillonite with stable interlamellar spacing;

[0033] The single alkenyl phenyl-POSS is prepared by first performing a Friedel-Crafts alkylation reaction of phenyl-POSS and 10-undecenol, and then performing a hydroxyl dehydration elimination reaction; then, under the action of a free radical initiator, the single alkenyl phenyl-POSS is grafted onto the main chain of polyethylene or polypropylene through a free radical addition reaction, so as to obtain phenyl-POSS functionalized polyethylene or phenyl-POSS functionalized polypropylene;

[0034] According to the Friedel-Crafts alkylation reaction mechanism, the phenyl-POSS functionalized polyethylene, the phenyl-POSS functionalized polypropylene and the alkenyl functionalized montmorillonite with stable interlamellar spacing are used as raw materials to prepare an organic-inorganic hybrid high-strength filler for modifying a polyolefin matrix;

[0035] Finally, a high-performance composite film is prepared by using an eleven-layer co-extrusion blow molding process, the mechanical properties of the high-performance composite film meet the standard of TB / T2689.4-2018 Railway Freight Containerization Transportation Part 4: Disposable Container Liquid Container Bag, and the comprehensive performance of the high-performance composite film is excellent, and the high-performance composite film has practical application value. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 Puncture resistance test results of the composite film for manufacturing a container liquid bag;

[0037] Figure 2 Nuclear magnetic resonance hydrogen spectrum of the single alkenyl phenyl-POSS;

[0038] Figure 3 Nuclear magnetic resonance hydrogen spectrum of the alkenyl gemini quaternary ammonium salt. DETAILED DESCRIPTION

[0039] The main raw materials used in the application are as follows:

[0040] Low-density polyethylene resin (LDPE), with a brand of LD 150DW;

[0041] Polypropylene resin (PP), with a brand of R520Y;

[0042] Maleic anhydride grafted polyethylene resin (PE-g-MAH), with a brand of 4288;

[0043] Metallocene polyethylene resin (m-LLDPE), brand SP1520;

[0044] Na-montmorillonite, with a flake diameter of 3-8 μm and a thickness of 5-15 nm;

[0045] Octaphenyl-POSS, CAS No. 5256-79-1.

[0046] Example One:

[0047] The composite film for manufacturing a container liquid bag I has the following layers arranged in sequence:

[0048] LDPE layer: formula 100wt% low density polyethylene resin, amount 10 parts by weight;

[0049] First TIE layer: formula 100wt% maleic anhydride grafted polyethylene resin, amount 4 parts by weight;

[0050] First PP layer: formula 100wt% polypropylene resin, amount 10 parts by weight;

[0051] Second TIE layer: formula 100wt% maleic anhydride grafted polyethylene resin, amount 4 parts by weight;

[0052] First PP-PE functional layer: formula 40wt% low density polyethylene resin and 60wt% organic-inorganic hybrid high-strength filler I, amount 20 parts by weight;

[0053] Third TIE layer: formula 100wt% maleic anhydride grafted polyethylene resin, amount 4 parts by weight;

[0054] Second PP-PE functional layer: formula 40wt% low density polyethylene resin and 60wt% organic-inorganic hybrid high-strength filler I, amount 20 parts by weight;

[0055] Fourth TIE layer: formula 100wt% maleic anhydride grafted polyethylene resin, amount 4 parts by weight;

[0056] Second PP layer: formula 100wt% polypropylene resin, amount 10 parts by weight;

[0057] Fifth TIE layer: formula 100wt% maleic anhydride grafted polyethylene resin, amount 4 parts by weight;

[0058] m-LLDPE layer: formula 100wt% metallocene polyethylene resin, amount 10 parts by weight;

[0059] The formula of the organic-inorganic hybrid high-strength filler I is: 30wt% of phenyl-POSS functionalized polyethylene, 30wt% of phenyl-POSS functionalized polypropylene, and 40wt% of alkenyl functionalized interlayer spacing stable montmorillonite.

[0060] The preparation method of the phenyl-POSS functionalized polyethylene is described in Experimental Example I below, the preparation method of the phenyl-POSS functionalized polypropylene is described in Experimental Example II below, and the preparation method of the alkenyl functionalized interlayer spacing stable montmorillonite is described in Experimental Example III below.

[0061] Example II:

[0062] The preparation process of the composite film I for manufacturing a container liquid bag includes the following steps:

[0063] Step 1: Preparation of the organic-inorganic hybrid high-strength filler I: under the action of a Lewis acid, Friedel-Crafts alkylation reaction occurs between the phenyl functional groups in the phenyl-POSS functionalized polyethylene and the phenyl-POSS functionalized polypropylene and the alkenyl functional groups on the surface of the alkenyl functionalized interlayer spacing stable montmorillonite, polyethylene and polypropylene are modified on the surface of the montmorillonite to form a coating layer, and the organic-inorganic hybrid high-strength filler I with a core-shell structure is prepared. The specific preparation steps are as follows: 3g of phenyl-POSS functionalized polyethylene, 3g of phenyl-POSS functionalized polypropylene, 4g of alkenyl functionalized interlayer spacing stable montmorillonite, and 0.2g of aluminum chloride are added to a high-speed mixer and mixed uniformly, and then added to a twin-screw extruder, melt processed for 20min, and extruded and granulated to obtain the organic-inorganic hybrid high-strength filler I;

[0064] The process parameters of the twin-screw extruder are set as follows: the preheating temperature is 170℃, and the temperatures of the 1-6 segments (in order: feeding segment, melting segment, plasticizing segment, exhaust segment, mixing segment, and extruding segment) are 170℃, 180℃, 185℃, 190℃, 205℃, and 200℃, respectively, and the rotation speed is 400r / min;

[0065] The Lewis acid can be selected from one of aluminum chloride, iron trichloride, tin tetrachloride, and zinc dichloride; and in this example, aluminum chloride is used;

[0066] Step 2: According to the formula of the composite film I for manufacturing a container liquid bag, the raw materials of each layer are respectively put into the hoppers of the eleven screw extruders of an eleven-layer co-extrusion film blowing machine set, the melt resins are converged at the die head through a flow divider, extruded, blown, and pulled (the blow-up ratio is controlled at 2.9), cooled, and wound to obtain the composite film I for manufacturing a container liquid bag;

[0067] The process parameters of the screw extruder corresponding to the LDPE layer and the m-LLDPE layer are set as follows: the temperatures of the first to third zones are 120 DEG C, 150 DEG C and 170 DEG C respectively, the flow channel temperature is 165 DEG C, and the rotating speed is 30 r / min;

[0068] The process parameters of the screw extruder corresponding to the TIE layer are set as follows: the temperatures of the first to third zones are 120 DEG C, 150 DEG C and 160 DEG C respectively, the flow channel temperature is 155 DEG C, and the rotating speed is 15 r / min;

[0069] The process parameters of the screw extruder corresponding to the PP layer are set as follows: the temperatures of the first to third zones are 130 DEG C, 160 DEG C and 185 DEG C respectively, the flow channel temperature is 180 DEG C, and the rotating speed is 40 r / min;

[0070] The process parameters of the screw extruder corresponding to the PP-PE functional layer are set as follows: the temperatures of the first to third zones are 150 DEG C, 180 DEG C and 205 DEG C respectively, the flow channel temperature is 200 DEG C, and the rotating speed is 60 r / min.

[0071] Example Three

[0072] The composite film II for manufacturing the liquid bag of the container is different from the composite film I for manufacturing the liquid bag of the container in example one only in that the organic-inorganic hybrid high-strength filler II is used to replace the organic-inorganic hybrid high-strength filler I;

[0073] The formula of the organic-inorganic hybrid high-strength filler II is as follows: 25wt% phenyl-POSS functionalized polyethylene, 25wt% phenyl-POSS functionalized polypropylene and 50wt% alkenyl functionalized interlayer spacing stable montmorillonite;

[0074] The preparation process of the composite film II for manufacturing the liquid bag of the container is the same as that of the composite film I for manufacturing the liquid bag of the container in example two.

[0075] Example Four

[0076] The composite film III for manufacturing the liquid bag of the container is different from the composite film I for manufacturing the liquid bag of the container in example one only in that the organic-inorganic hybrid high-strength filler III is used to replace the organic-inorganic hybrid high-strength filler I;

[0077] The formula of the organic-inorganic hybrid high-strength filler III is as follows: 20wt% phenyl-POSS functionalized polyethylene, 20wt% phenyl-POSS functionalized polypropylene and 60wt% alkenyl functionalized interlayer spacing stable montmorillonite;

[0078] The preparation process of the composite film for manufacturing the container liquid bag III is the same as that of the composite film for manufacturing the container liquid bag I in Example 2.

[0079] Comparative Example:

[0080] Preparation of a conventional composite film: the difference between it and the composite film for manufacturing the container liquid bag I is only that the formulation of the PP-PE functional layer is 100 wt% low-density polyethylene resin (without using organic-inorganic hybrid high-strength fillers), and the amount is 20 parts by weight.

[0081] Performance test:

[0082] I. Mechanical property test of the composite film for manufacturing the container liquid bag sample, the test result index is TB / T 2689.4-2018 “Railway Freight Containerization Transportation Part 4: Disposable Container Liquid Container Bag”, and the test results are shown in Tables 1, 2 and Figure 1

[0083] Table 1 Performance test results of the composite film for manufacturing the container liquid bag

[0084]

[0085] Table 2 Performance test results of the composite film for manufacturing the container liquid bag

[0086]

[0087] II. Barrier property and heat sealing property test of the composite film for manufacturing the container liquid bag sample, as follows:

[0088] (1) Barrier property: test the oxygen transmission amount and water vapor transmission amount of the sample according to GB / T 1038.1-2022 “Plastic Products Film and Sheet Gas Permeability Test Method Part 1: Differential Pressure Method” and GB / T 1037-2021 “Plastic Film and Sheet Water Vapor Transmission Performance Test Cup Weight Gain and Weight Loss Method” standards;

[0089] (2) Heat sealing property: heat sealing experiment is performed on the sample, the knife area is 15 cm x 1 cm, the heat sealing temperature is 120℃, the heat sealing pressure is 0.2 MPa, and the heat sealing time is 2.0 s; the heat sealing strength of the heat sealing sample is tested according to QB / T 2358-1998 “Plastic Film Packaging Bag Heat Sealing Strength Test Method”, the test speed is 100 mm / min, and the clamp spacing is 50 mm;

[0090] The above test results are shown in Table 3;

[0091] ​Table 3 Performance test results of the composite film for manufacturing a container liquid bag

[0092]

[0093] Through comprehensive analysis of the above experimental results, the following conclusions can be drawn:

[0094] Conclusion 1: The composite film product prepared by using the self-developed organic-inorganic hybrid high-strength filler has significantly improved mechanical properties and barrier properties compared to conventional composite films.

[0095] Conclusion 2: The mechanical properties of the composite film product for manufacturing a container liquid bag prepared by the present application meet the national standard requirements, and the comprehensive performance is excellent, having practical application value.

[0096] Experimental Example 1

[0097] Preparation of phenyl-POSS functionalized polyethylene: free radicals are generated by low-density polyethylene resin under the action of a peroxide initiator, and the addition reaction of the alkenyl functional group in monoalkenyl phenyl-POSS with the free radicals in the low-density polyethylene resin is used to realize the graft modification treatment of the low-density polyethylene resin, and phenyl-POSS functionalized polyethylene is obtained. The specific preparation steps are as follows: first, dry the low-density polyethylene resin in a 50℃ vacuum drying oven for 12h, then add 9g of the dried low-density polyethylene resin, 1g of monoalkenyl phenyl-POSS, and 0.1g of dicumyl peroxide initiator into a high-speed mixer and mix uniformly, and then add them into a twin-screw extruder for grafting reaction by high-temperature melt mixing. After 10min of melt processing in the twin-screw extruder and extrusion granulation, phenyl-POSS functionalized polyethylene is obtained.

[0098] The process parameters of the twin-screw extruder are set as follows: preheating temperature 150℃, and temperatures of 1-6 segments (in order: feeding segment, melting segment, plasticizing segment, exhaust segment, mixing segment, and extrusion segment) are 150℃, 160℃, 170℃, 180℃, 180℃, and 175℃, respectively, and the rotation speed is 200r / min.

[0099] The peroxide initiator can be one of dicumyl peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide, and tert-butyl benzoate peroxide. Dicumyl peroxide is used in this experimental example.

[0100] The synthesis method of monoalkenyl phenyl-POSS includes but is not limited to the following reaction steps:

[0101] Step 1: Using octaphenyl-POSS as a base material, a Friedel-Crafts alkylation reaction is carried out under the action of a Lewis acid via the alkenyl functional group of 10-undecenol and the phenyl functional group of octaphenyl-POSS. The molar ratio of octaphenyl-POSS to 10-undecenol is controlled at 1:0.92 to generate monohydroxyphenyl-POSS, whose chemical structural formula is as follows:

[0102] ;

[0103] The Lewis acid can be selected from aluminum trichloride, ferric chloride, tin tetrachloride, and zinc dichloride; aluminum trichloride was chosen for this experimental example.

[0104] Step 2: Under the action of sulfate, the hydroxyl functional group of monohydroxyphenyl-POSS undergoes a dehydration elimination reaction to generate monoalkenylphenyl-POSS, whose chemical structural formula is as follows:

[0105] ;

[0106] The sulfate can be selected from aluminum sulfate, zirconium sulfate, or potassium bisulfate; this experimental example uses zirconium sulfate.

[0107] The specific experimental steps for synthesizing monoalkenylphenyl-POSS are as follows:

[0108] 5.2 g of octaphenyl-POSS, 0.8 g of 10-undecenol, 1.5 g of anhydrous aluminum trichloride and 50 mL of 1,2-dichloroethane were added to a three-necked flask, heated to 85 °C and stirred under reflux for 24 h, cooled to room temperature, evaporated under reduced pressure, washed with deionized water and dried to obtain monohydroxyphenyl-POSS.

[0109] 3.0 g of monohydroxyphenyl-POSS, 1.8 g of zirconium sulfate and 50 mL of xylene were added to a three-necked flask, heated to 120 °C and stirred for 24 h, cooled to room temperature, evaporated under reduced pressure, washed with deionized water and dried to obtain monoalkenylphenyl-POSS;

[0110] like Figure 2 As shown, the 1H NMR spectrum of monoalkenylphenyl-POSS is characterized as follows: 1 H NMR (CDCl3, 400MHz) δ: 1.20-1.40 (m, 12H), 1.58-1.65 (m, 2H), 2.01-2.06 (m, 2H), 2.61-2.65 (t, 2H), 4.94-5.10 (dd, 2H), 5.74-5.84 (m, 1H), 7.16-7.54 (m, 39H).

[0111] Experimental Example 2:

[0112] Preparation of phenyl-POSS functionalized polypropylene: free radicals are generated by polypropylene resin under the action of peroxide initiator, and the addition reaction of alkenyl functional groups in monoalkenyl phenyl-POSS with free radicals in low density polyethylene resin is used to realize the graft modification of polypropylene resin, and phenyl-POSS functionalized polypropylene is obtained. The specific preparation steps are as follows: first, the polypropylene resin is dried in a vacuum drying box at 60°C for 12h, then 9g of dried polypropylene resin, 1g of monoalkenyl phenyl-POSS and 0.1g of dicumyl peroxide initiator are added into a high-speed mixer and mixed uniformly, and then added into a twin-screw extruder for grafting reaction by high-temperature melt mixing. After 15min of melt processing in the twin-screw extruder, the product is extruded and granulated to obtain phenyl-POSS functionalized polypropylene;

[0113] The process parameters of the twin-screw extruder are set as follows: preheating temperature 160°C, and temperatures of 1-6 segments (in order: feeding segment, melting segment, plasticizing segment, exhaust segment, mixing segment, and extruding segment) are 160°C, 170°C, 180°C, 190°C, 195°C, and 190°C, respectively, and the rotating speed is 300r / min;

[0114] The peroxide initiator can be selected from one of dicumyl peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide, and tert-butyl peroxybenzoate. In this experimental example, dicumyl peroxide is used.

[0115] The synthesis method of monoalkenyl phenyl-POSS is the same as that in Experimental Example One.

[0116] Experimental Example Three:

[0117] Preparation of alkenyl functionalized interlamellar spacing stable montmorillonite: the interlamellar spacing stable montmorillonite is modified by using alkenyl gemini quaternary ammonium salt. The ammonium cation of the alkenyl gemini quaternary ammonium salt first undergoes ion exchange with the sodium cation in the interlamellar spacing of the sodium-based montmorillonite, and then is adsorbed on the surface of the montmorillonite nanosheet through electrostatic interaction to obtain the alkenyl functionalized interlamellar spacing stable montmorillonite. The specific preparation steps are as follows: 5g of sodium-based montmorillonite and 80mL of anhydrous N,N-dimethylformamide are added into a three-necked flask, ultrasonic treatment for 30min, and then heated to 70°C for stirring and dispersion for 2h. Then 20mL of anhydrous N,N-dimethylformamide solution containing 1g of alkenyl gemini quaternary ammonium salt is added into the three-necked flask, and the stirring reaction is carried out at 70°C for 6h. After filtration, the product is washed with anhydrous ethanol until no precipitate is detected in silver nitrate solution. After drying, the alkenyl functionalized interlamellar spacing stable montmorillonite is obtained.

[0118] The synthesis method of the alkenyl gemini quaternary ammonium salt includes but is not limited to the following reaction formula and reaction steps:

[0119] ;

[0120] Step 1: An amino-enyl addition reaction occurs between the amino functional group of 3-amino-1-propanol and the alkenyl functional group of methacryloyloxyethyltrimethylammonium chloride, and the molar ratio of 3-amino-1-propanol to methacryloyloxyethyltrimethylammonium chloride is controlled to be 1:2.06 to generate the hydroxyammonium chloride monomer.

[0121] Step 2: A nucleophilic substitution reaction occurs between the hydroxyl functional group of the ammonium hydroxychloride monomer and the acyl chloride functional group of 10-undecenoyl chloride, and the molar ratio of ammonium hydroxychloride monomer to 10-undecenoyl chloride is controlled to be 1:1.03 to generate an alkenylated gemini quaternary ammonium salt.

[0122] The specific experimental steps for synthesizing alkenylated gemini quaternary ammonium salts are as follows:

[0123] 0.7 g of 3-amino-1-propanol and 10 mL of anhydrous N,N-dimethylformamide were added to a three-necked flask and stirred at room temperature until completely dissolved. Then, 40 mL of anhydrous N,N-dimethylformamide solution containing 4.1 g of methacryloyloxyethyltrimethylammonium chloride was added to the three-necked flask and stirred at room temperature for 30 min. The mixture was then heated to 60 °C and stirred for 4 h. After cooling to room temperature, the mixture was evaporated under reduced pressure and dried to obtain the hydroxyammonium chloride monomer.

[0124] 2.4 g of ammonium hydroxide monomer and 20 mL of anhydrous N,N-dimethylformamide were added to a three-necked flask and stirred at room temperature until completely dissolved. Under nitrogen protection, 10 mL of anhydrous N,N-dimethylformamide solution containing 1.0 g of 10-undecenoyl chloride was added to the three-necked flask. The mixture was heated to 40 °C and stirred for 6 h. After cooling to room temperature, 1.5 mL of 5 wt% sodium carbonate aqueous solution was added dropwise. The mixture was then rotary evaporated under reduced pressure, washed with deionized water, and dried to obtain an alkenylated gemini quaternary ammonium salt.

[0125] like Figure 3 As shown, the 1H NMR characterization of the alkenylated gemini quaternary ammonium salt is as follows: 1 H NMR (CDCl3, 400MHz) δ: 1.17-1.19 (d, 6H), 1.25-1.42 (m, 12H), 1.82-1.89 (m, 2H), 2.01-2.06 (m, 2H), 2.29-2.32 (t, 2H), 2.49-2.58 (m, 2H), 2.62 -2.65(t, 2H), 2.79-2.81(d, 4H), 3.36(s, 18H), 3.71-3.74(t, 4H), 4.07 -4.11 (t, 2H), 4.35-4.39 (t, 4H), 4.95-5.10 (dd, 2H), 5.74-5.84 (m, 1H).

Claims

1. A composite film for manufacturing a container bag, characterized by, The product structure of the composite film is: LDPE layer / TIE layer / PP layer / TIE layer / PP-PE functional layer / TIE layer / PP-PE functional layer / TIE layer / PP layer / TIE layer / m-LLDPE layer. The formula of the LDPE layer is 100wt% low-density polyethylene resin, and the amount is 5-15 parts by weight; The formula of the TIE layer is 100wt% maleic anhydride grafted polyethylene resin, and the amount is 1-5 parts by weight; The formula of the PP layer is 100wt% polypropylene resin, and the amount is 5-15 parts by weight; The formula of the PP-PE functional layer is 30-50wt% low-density polyethylene resin and 50-70wt% organic-inorganic hybrid high-strength filler, and the amount is 15-25 parts by weight; The formula of the organic-inorganic hybrid high-strength filler is: 20-30wt% phenyl-POSS functionalized polyethylene, 20-30wt% phenyl-POSS functionalized polypropylene, and 40-60wt% alkenyl functionalized interlayer spacing stable montmorillonite; wherein the phenyl-POSS functionalized polyethylene is prepared by grafting a monoalkenyl phenyl-POSS onto a polyethylene main chain through a free radical addition reaction; the phenyl-POSS functionalized polypropylene is prepared by grafting a monoalkenyl phenyl-POSS onto a polypropylene main chain through a free radical addition reaction; and the alkenyl functionalized interlayer spacing stable montmorillonite is prepared by intercalating modification of sodium-based montmorillonite with an alkenyl gemini quaternary ammonium salt through an ion exchange reaction; The chemical structural formula of the alkenyl gemini quaternary ammonium salt is: ； The chemical structural formula of the monoalkenyl phenyl-POSS is: ； The formula of the m-LLDPE layer is 100wt% metallocene polyethylene resin, and the amount is 5-15 parts by weight.

2. The composite film for manufacturing a container bag according to claim 1, wherein The thickness of the composite film is 130-180μm.

3. The composite film for manufacturing a container liquid bag according to claim 1, wherein The mass ratio of the alkenyl gemini quaternary ammonium salt to the sodium-based montmorillonite in the alkenyl functionalized interlayer spacing stable montmorillonite is 1:(3-8).

4. The composite film for manufacturing a container bag according to claim 3, wherein The flake diameter of the sodium-based montmorillonite is 3-8μm, and the thickness is 5-15nm.

5. The composite film for manufacturing a container liquid bag according to claim 1, wherein The mass ratio of the monoalkenyl phenyl-POSS to the polyethylene in the phenyl-POSS functionalized polyethylene is 1:(8-10); The mass ratio of the monoalkenyl phenyl-POSS to the polypropylene in the phenyl-POSS functionalized polypropylene is 1:(8-10).

6. The manufacturing process for manufacturing a composite film for a container liquid bag according to any one of claims 1 to 5, characterized in that, The method comprises the following steps: Step one: synthesizing a monoalkenyl phenyl-POSS, and sequentially functionalizing and modifying polyethylene and polypropylene with the monoalkenyl phenyl-POSS to sequentially prepare phenyl-POSS functionalized polyethylene and phenyl-POSS functionalized polypropylene; synthesizing an alkenyl gemini quaternary ammonium salt, and functionalizing and modifying sodium-based montmorillonite with the alkenyl gemini quaternary ammonium salt to prepare alkenyl functionalized interlayer spacing stable montmorillonite; under the action of a Lewis acid, Friedel-Crafts alkylation occurs between the phenyl functional groups in the phenyl-POSS functionalized polyethylene and the phenyl-POSS functionalized polypropylene and the alkenyl functional groups on the surface of the alkenyl functionalized interlayer spacing stable montmorillonite, polyethylene and polypropylene are grafted on the surface of the montmorillonite, and an organic-inorganic hybrid high-strength filler is prepared; Step two: according to the formula of the composite film, ingredients are prepared, and each layer of raw material is respectively put into the hopper of the eleven screw extruders of the eleven-layer co-extrusion film blowing machine unit, the molten resin is converged at the die head through the flow divider, extruded, blown and pulled through the die, cooled and rolled to prepare the composite film for manufacturing the container liquid bag.

7. The manufacturing process for manufacturing a composite film for a container liquid bag according to claim 6, wherein The preparation method of the alkenylated Gemini quaternary ammonium salt is: An amine-alkene addition reaction occurs between the amino functional group of 3-amino-1-propanol and the alkenyl functional group of methacryloyloxyethyl trimethyl ammonium chloride, and the molar ratio of 3-amino-1-propanol to methacryloyloxyethyl trimethyl ammonium chloride is controlled to be 1:2.05-2.09, to generate a hydroxyl ammonium chloride monomer; A nucleophilic substitution reaction occurs between the hydroxyl functional group of the hydroxyl ammonium chloride monomer and the acyl chloride functional group of 10-undecenoyl chloride, and the molar ratio of the hydroxyl ammonium chloride monomer to 10-undecenoyl chloride is controlled to be 1:1.01-1.05, to generate the alkenylated Gemini quaternary ammonium salt.

8. The manufacturing process for manufacturing a composite film for a container liquid bag according to claim 6, wherein, The preparation method of the monoalkenyl phenyl-POSS is: Under the action of a Lewis acid, a Friedel-Crafts alkylation reaction occurs between the alkenyl functional group of 10-undecenol and the phenyl functional group of octaphenyl-POSS, and the molar ratio of octaphenyl-POSS to 10-undecenol is controlled to be 1:0.91-0.95, to generate mono-hydroxyphenyl-POSS; Under the action of a sulfate, a dehydration elimination reaction occurs between the hydroxyl functional group of mono-hydroxyphenyl-POSS, to generate mono-alkenyl phenyl-POSS.

9. The manufacturing process for manufacturing a composite film for a container liquid bag according to claim 8, wherein, The Lewis acid is one of aluminum chloride, iron trichloride, tin tetrachloride, and zinc dichloride.

10. The manufacturing process for manufacturing a composite film for a container liquid bag according to claim 8, wherein, The sulfate is one of aluminum sulfate, zirconium sulfate, and potassium hydrogen sulfate.

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