CN119119614A - A high-strength polyethylene milk bottle cap and its preparation process - Google Patents
A high-strength polyethylene milk bottle cap and its preparation process Download PDFInfo
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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Abstract
本发明涉及牛奶瓶盖技术领域，具体为一种高强度聚乙烯牛奶瓶盖及其制备工艺。步骤1：功能添加剂的制备：S1：将聚赖氨酸加入至纳米蒙脱土分散液中，在60~65℃下插层反应2~3小时，离心、干燥，得到改性纳米蒙脱土；S2：氮气氛围下，将咖啡酸加入至PBS缓冲溶液中，加入EDC、NHS，在冰浴下搅拌15~30分钟；加入改性纳米蒙脱土‑PBS缓冲溶液，继续搅拌24小时，洗涤干燥，得到功能添加剂；步骤2：将高密度聚乙烯、功能添加剂、相容剂、醛基化聚烯烃弹性体、棕榈油、色母混合，熔融挤出，注塑成型，得到高强度聚乙烯牛奶瓶盖。方案中，制备得到的高强度聚乙烯牛奶瓶盖具有优异力学强度和氧阻隔性。The present invention relates to the technical field of milk bottle caps, specifically a high-strength polyethylene milk bottle cap and a preparation process thereof. Step 1: Preparation of functional additives: S1: Add polylysine to a nano-montmorillonite dispersion, perform intercalation reaction at 60-65°C for 2-3 hours, centrifuge and dry to obtain modified nano-montmorillonite; S2: Under a nitrogen atmosphere, add caffeic acid to a PBS buffer solution, add EDC and NHS, and stir in an ice bath for 15-30 minutes; add modified nano-montmorillonite-PBS buffer solution, continue stirring for 24 hours, wash and dry to obtain a functional additive; Step 2: Mix high-density polyethylene, functional additives, compatibilizers, aldehyde-modified polyolefin elastomers, palm oil, and masterbatches, melt extrude, and injection mold to obtain a high-strength polyethylene milk bottle cap. In the scheme, the prepared high-strength polyethylene milk bottle cap has excellent mechanical strength and oxygen barrier properties.
Description
Technical Field
The invention relates to the technical field of milk bottle caps, in particular to a high-strength polyethylene milk bottle cap and a preparation process thereof.
Background
In recent years, with the increasing consumer demands for food safety and packaging quality, the market demand for high strength, high sealing properties has grown. Polyethylene is a thermoplastic material with wide application, and is an ideal material for manufacturing milk bottle caps due to light weight, durability and high chemical stability. However, the traditional polyethylene bottle cap has the defects of insufficient rigidity and toughness, poor oxidation resistance and barrier property, and can produce the problems of aging, deformation and the like under the addition of high temperature or illumination and the like, thereby reducing the sealing performance of the bottle cap and affecting the preservation and transportation of milk.
In order to ensure the quality of milk and prolong the shelf life, the oxidation resistance and the barrier property of the polyethylene bottle cap need to be comprehensively improved. In the prior art, antioxidants such as butyl hydroxy anisole and blocking agents such as montmorillonite are generally introduced, firstly, migration and dispersibility problems exist, potential safety hazards exist, and secondly, compatibility problems exist, so that the mechanical properties of the polyethylene bottle cap are influenced due to excessive introduced quantity.
In summary, the preparation of the high-strength polyethylene milk bottle cap has important significance in solving the problems.
Disclosure of Invention
The invention aims to provide a high-strength polyethylene milk bottle cap and a preparation process thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
A preparation process of a high-strength polyethylene milk bottle cap comprises the following steps:
Step 1, preparing a functional additive:
S1, adding polylysine into nano montmorillonite dispersion liquid, performing intercalation reaction for 2-3 hours at 60-65 ℃, centrifuging and drying to obtain modified nano montmorillonite;
S2, adding caffeic acid into PBS buffer solution under nitrogen atmosphere, adding EDC and NHS, stirring for 15-30 minutes in ice bath, adding modified nano montmorillonite-PBS buffer solution, continuously stirring for 24 hours, washing and drying to obtain a functional additive;
And 2, mixing the high-density polyethylene, the functional additive, the compatilizer, the aldehyde polyolefin elastomer, the palm oil and the color master batch, performing melt extrusion, and performing injection molding to obtain the high-strength polyethylene milk bottle cap.
More optimally, the raw materials of the high-strength polyethylene milk bottle cap comprise, by weight, 100 parts of high-density polyethylene, 4-8 parts of functional additives, 2-5 parts of compatilizers, 1.5-3 parts of aldehyde polyolefin elastomers, 1-1.5 parts of palm oil and 1-2 parts of color concentrates.
More preferably, the compatilizer comprises maleic anhydride grafted polyethylene and maleic anhydride grafted polyolefin elastomer with the mass of 2:3.
More optimally, the modified nano montmorillonite comprises polylysine and nano montmorillonite with the mass ratio of 4:3.2-3.5, and the functional additive comprises modified nano montmorillonite and caffeic acid with the mass ratio of 1:0.2-0.3.
More optimally, the preparation method of the modified polyolefin elastomer comprises the following steps:
S1, melting and extruding a polyolefin elastomer, 4-vinyl benzyl alcohol and a peroxidation initiator in a double screw base, and grinding the components to obtain a hydroxylation modified polyolefin elastomer;
And S2, sequentially adding the hydroxylation modified polyolefin elastomer and the molybdenum catalyst into DMF, reacting for 2-3 hours at 50-55 ℃, washing and drying to obtain the aldehyde polyolefin elastomer.
More optimally, the hydroxylation modified polyolefin elastomer comprises a polyolefin elastomer, 4-vinyl benzyl alcohol and a peroxidation initiator in a mass ratio of 90:5-10:0.1-0.5;
the aldehyde polyolefin elastomer comprises a hydroxylation modified polyolefin elastomer and a molybdenum catalyst in a mass ratio of 1:0.02-0.05.
The preparation method of the molybdenum catalyst comprises the steps of sequentially adding dichloro molybdenum dioxide and carbon black with the mass ratio of 1:1 into DMF, reacting for 24 hours at 115-120 ℃, washing and drying to obtain the molybdenum catalyst.
More preferably, the functional additive is pre-compounded with the aldehyde polyolefin elastomer, and the process of the step 2 is as follows:
S1, dispersing a functional additive and an aldehyde polyolefin elastomer in ethanol in sequence, stirring and heating for 4-6 hours at 60-65 ℃, removing solvent, and drying to obtain a raw material A;
and S2, mixing the raw material A with high-density polyethylene, a compatilizer, palm oil and a color master batch, and performing melt extrusion and injection molding to obtain the high-strength polyethylene milk bottle cap.
More optimally, the technological parameters of melt extrusion are that the feeding rate is 10-15 r/min, the screw rotating speed is 30-40 r/min, the temperatures of all the temperature areas are 165-170 ℃, 175-180 ℃, 185-190 ℃ and 175-180 ℃, the technological parameters of injection molding are that the injection molding pressure is 80-100 bar, and the temperatures of all the temperature areas are 200-205 ℃, 210-215 ℃, 215-220 ℃ and 215-220 ℃.
More optimally, the high-strength polyethylene milk bottle cap is prepared by the preparation process of the high-strength polyethylene milk bottle cap.
Compared with the prior art, the functional additive has the beneficial effects that the functional additive prepared in the scheme obviously enhances the oxidation resistance and the barrier property of the polyethylene milk bottle cap, and simultaneously two compatilizers are used for the dispersibility and the compatibility of the functional additive in the polyethylene milk bottle cap. In addition, the aldehyde polyolefin elastomer modified functional additive is introduced, so that the interface performance of the functional additive is further enhanced, the introduced amount of the functional additive is increased, the migration is inhibited, and the mechanical property and the barrier property of the polyethylene milk bottle cap are improved.
In the scheme, the functional additive is based on nano montmorillonite, polylysine is loaded on the nano montmorillonite through intercalation reaction, and caffeic acid is grafted on the polylysine by further utilizing the reaction of carboxyl and amino, so that the functional additive is obtained in sequence.
The nano montmorillonite is natural lamellar silicate with bacteriostasis, has a lamellar structure with high aspect ratio and no permeability, and can effectively reduce the diffusion path of molecules, thereby improving the antibacterial property and the oxygen barrier property. Meanwhile, the introduction of the polyethylene neumai bottle cap can promote the crystallization form of the polymer, thereby effectively enhancing the strength of the polyethylene neumai bottle cap. The polylysine is a safe material with antibacterial and antioxidant properties, the antibacterial and barrier properties of the functional additive are further improved, the antioxidant properties are increased, the functional additive further contains amino groups as functional sites, caffeic acid is further grafted, the caffeic acid is a polyphenol compound, the antioxidant activity is limited, the oxidation reaction can be inhibited, the shelf life of milk is prolonged, and meanwhile, the caffeic acid contains vinyl groups and can be crosslinked with high-density polyethylene.
In the scheme, in order to further improve the dispersibility of the functional additive in the high-density polyethylene, the mechanical property of the milk bottle cap is improved. In the scheme, amino sites contained in the functional additive are utilized to further react and graft with the aldehyde polyolefin elastomer, and the polyolefin elastomer chain segments in the aldehyde polyolefin elastomer are effectively dispersed in the high-density polyethylene, so that the interface effect is further improved. Meanwhile, the aldehyde polyolefin elastomer has toughness to high-density polyethylene, and is prepared by grafting 4-vinyl benzyl alcohol firstly and converting alcohol groups into aldehyde groups by using a catalyst, and the benzene ring in the 4-vinyl benzyl alcohol has rigidity, so that the tensile strength of the polyethylene bottle cap can be improved by introducing the aldehyde polyolefin elastomer.
The application further introduces a compound compatilizer for further improving the performance, wherein the compound compatilizer comprises maleic anhydride grafted polyethylene and maleic anhydride grafted polyolefin elastomer, the maleic anhydride grafted polyolefin elastomer can further improve the dispersibility of the functional additive, the synergistic hydroformylation polyolefin elastomer is effectively arranged in an interface structure, the interface of the elastomer is ensured, the introduction of the maleic anhydride grafted polyethylene ensures the interface strength of the composite material, and compared with the single compatilizer, the specific proportion of the maleic anhydride grafted polyethylene and the maleic anhydride grafted polyolefin elastomer is introduced to ensure that the polyethylene milk bottle cap has higher mechanical strength. In addition, palm oil is introduced as a plasticizer to improve the processability of the high-strength polyethylene milk bottle cap.
Detailed Description
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials used in the invention are not particularly limited, and include, for example, high-density polyethylene, such as HD2200JP, PTT, XH6050MGXTTR, VA-1202, ekson palm oil, tengyun chemical, 8001, dude plastic, 8003, american Dow, PBS buffer solution, food grade, carnobilis, van, buddha, coffee acid, CAS No. 331-39-5, 4-vinyl benzyl alcohol, and CAS No. 1074-61-9, respectively.
The preparation of the molybdenum catalyst comprises the steps of sequentially adding dichloro molybdenum dioxide and carbon black with the mass ratio of 1:1 into DMF, reacting for 24 hours at 120 ℃, washing and drying to obtain the molybdenum catalyst.
Embodiment 1a preparation process of a high-strength polyethylene milk bottle cap comprises the following steps:
The preparation method comprises the steps of S1, adding 4 parts of polylysine into 3.2g/L nano montmorillonite dispersion liquid (containing 3.2 parts of nano montmorillonite and deionized water as solvent), conducting intercalation reaction for 2 hours at 65 ℃, centrifuging and drying to obtain modified nano montmorillonite, S2, adding 0.3 part of caffeic acid into 30 parts of PBS buffer solution under nitrogen atmosphere, adding 0.3 part of EDC and 0.18 part of NHS, stirring for 30 minutes under ice bath, adding modified nano montmorillonite-PBS buffer solution (1 part of modified nano montmorillonite and 30 parts of PBS buffer solution), continuing stirring for 24 hours, washing and drying to obtain the functional additive;
step 2, preparing a high-strength polyethylene milk bottle cap:
the preparation method comprises the steps of S1, (1) melting and extruding 9 parts of polyolefin elastomer, 1 part of 4-vinyl benzyl alcohol and 0.3 part of peroxidation initiator BPO in a double screw base, grinding components to obtain a hydroxylated modified polyolefin elastomer, (2) sequentially adding the hydroxylated modified polyolefin elastomer and a molybdenum catalyst in a mass ratio of 1:0.04 into DMF, reacting for 2 hours at 55 ℃, washing and drying to obtain the hydroformylation polyolefin elastomer;
s2, weighing 100 parts of high-density polyethylene, 6 parts of functional additive, 3 parts of compatilizer (maleic anhydride grafted polyethylene and maleic anhydride grafted polyolefin elastomer with the mass ratio of 2:3), 3 parts of aldehyde polyolefin elastomer, 1.5 parts of palm oil and 1.5 parts of color masterbatch as raw materials;
s3, (1) dispersing the functional additive and the aldehyde polyolefin elastomer in 100 parts of ethanol in turn, stirring and heating for 6 hours at 65 ℃, removing the solvent, and drying to obtain a raw material A;
(2) Mixing the raw material A with high-density polyethylene, a compatilizer, palm oil and a color master batch, setting the technological parameters of feeding rate of 10r/min, screw rotating speed of 35r/min, carrying out melt extrusion at the temperatures of 165 ℃, 170 ℃, 175 ℃, 185 ℃ and 175 ℃ in each temperature region, and setting the technological parameters of injection molding at the injection pressure of 80bar, and carrying out injection molding at the temperatures of 200 ℃,210 ℃, 215 ℃ and 220 ℃ in each temperature region to obtain the high-strength polyethylene milk bottle cap.
Embodiment 2 a preparation process of a high-strength polyethylene milk bottle cap comprises the following steps:
The preparation method comprises the steps of S1, adding 4 parts of polylysine into 3.2g/L nano montmorillonite dispersion liquid (containing 3.2 parts of nano montmorillonite and deionized water as solvent), conducting intercalation reaction for 2 hours at 65 ℃, centrifuging and drying to obtain modified nano montmorillonite, S2, adding 0.3 part of caffeic acid into 30 parts of PBS buffer solution under nitrogen atmosphere, adding 0.3 part of EDC and 0.18 part of NHS, stirring for 30 minutes under ice bath, adding modified nano montmorillonite-PBS buffer solution (1 part of modified nano montmorillonite and 30 parts of PBS buffer solution), continuing stirring for 24 hours, washing and drying to obtain the functional additive;
step 2, preparing a high-strength polyethylene milk bottle cap:
the preparation method comprises the steps of S1, (1) melting and extruding 9 parts of polyolefin elastomer, 1 part of 4-vinyl benzyl alcohol and 0.3 part of peroxidation initiator BPO in a double screw base, grinding components to obtain a hydroxylated modified polyolefin elastomer, (2) sequentially adding the hydroxylated modified polyolefin elastomer and a molybdenum catalyst in a mass ratio of 1:0.04 into DMF, reacting for 2 hours at 55 ℃, washing and drying to obtain the hydroformylation polyolefin elastomer;
s2, weighing 100 parts of high-density polyethylene, 4 parts of functional additive, 2 parts of compatilizer (maleic anhydride grafted polyethylene and maleic anhydride grafted polyolefin elastomer with the mass ratio of 2:3), 1.5 parts of aldehyde polyolefin elastomer, 1.5 parts of palm oil and 1 part of color masterbatch as raw materials;
s3, (1) dispersing the functional additive and the aldehyde polyolefin elastomer in 100 parts of ethanol in turn, stirring and heating for 6 hours at 65 ℃, removing the solvent, and drying to obtain a raw material A;
(2) Mixing the raw material A with high-density polyethylene, a compatilizer, palm oil and a color master batch, setting the technological parameters of feeding rate of 10r/min, screw rotating speed of 30r/min, carrying out melt extrusion at the temperatures of 165 ℃, 170 ℃, 175 ℃, 185 ℃ and 175 ℃ in each temperature region, and setting the technological parameters of injection molding at the injection pressure of 80bar, and carrying out injection molding at the temperatures of 200 ℃,210 ℃, 215 ℃ and 220 ℃ in each temperature region to obtain the high-strength polyethylene milk bottle cap.
Embodiment 3a preparation process of a high-strength polyethylene milk bottle cap comprises the following steps:
The preparation method comprises the steps of S1, adding 4 parts of polylysine into 3.2g/L nano montmorillonite dispersion liquid (containing 3.2 parts of nano montmorillonite and deionized water as solvent), conducting intercalation reaction for 2 hours at 65 ℃, centrifuging and drying to obtain modified nano montmorillonite, S2, adding 0.3 part of caffeic acid into 30 parts of PBS buffer solution under nitrogen atmosphere, adding 0.3 part of EDC and 0.18 part of NHS, stirring for 30 minutes under ice bath, adding modified nano montmorillonite-PBS buffer solution (1 part of modified nano montmorillonite and 30 parts of PBS buffer solution), continuing stirring for 24 hours, washing and drying to obtain the functional additive;
step 2, preparing a high-strength polyethylene milk bottle cap:
the preparation method comprises the steps of S1, (1) melting and extruding 9 parts of polyolefin elastomer, 1 part of 4-vinyl benzyl alcohol and 0.3 part of peroxidation initiator BPO in a double screw base, grinding components to obtain a hydroxylated modified polyolefin elastomer, (2) sequentially adding the hydroxylated modified polyolefin elastomer and a molybdenum catalyst in a mass ratio of 1:0.04 into DMF, reacting for 2 hours at 55 ℃, washing and drying to obtain the hydroformylation polyolefin elastomer;
S2, weighing 100 parts of high-density polyethylene, 8 parts of functional additive, 5 parts of compatilizer (maleic anhydride grafted polyethylene and maleic anhydride grafted polyolefin elastomer with the mass ratio of 2:3), 3 parts of aldehyde polyolefin elastomer, 1 part of palm oil and 2 parts of color masterbatch as raw materials;
s3, (1) dispersing the functional additive and the aldehyde polyolefin elastomer in 100 parts of ethanol in turn, stirring and heating for 6 hours at 65 ℃, removing the solvent, and drying to obtain a raw material A;
(2) Mixing the raw material A with high-density polyethylene, a compatilizer, palm oil and a color master batch, setting the technological parameters of feeding rate of 10r/min, screw rotating speed of 40r/min, carrying out melt extrusion at the temperatures of 165 ℃, 170 ℃, 175 ℃, 185 ℃ and 175 ℃ in each temperature region, and setting the technological parameters of injection molding at the injection pressure of 100bar, and carrying out injection molding at the temperatures of 200 ℃, 210 ℃, 215 ℃ and 220 ℃ in each temperature region to obtain the high-strength polyethylene milk bottle cap.
Comparative example 1 based on example 1, a polyolefin elastomer was used instead of the aldehyde polyolefin elastomer, the remainder being the same as example 1;
The preparation method comprises the steps of S1, adding 4 parts of polylysine into 3.2g/L nano montmorillonite dispersion liquid (containing 3.2 parts of nano montmorillonite and deionized water as solvent), conducting intercalation reaction for 2 hours at 65 ℃, centrifuging and drying to obtain modified nano montmorillonite, S2, adding 0.3 part of caffeic acid into 30 parts of PBS buffer solution under nitrogen atmosphere, adding 0.3 part of EDC and 0.18 part of NHS, stirring for 30 minutes under ice bath, adding modified nano montmorillonite-PBS buffer solution (1 part of modified nano montmorillonite and 30 parts of PBS buffer solution), continuing stirring for 24 hours, washing and drying to obtain the functional additive;
step 2, preparing a high-strength polyethylene milk bottle cap:
s1, weighing 100 parts of high-density polyethylene, 6 parts of functional additive, 3 parts of compatilizer (maleic anhydride grafted polyethylene and maleic anhydride grafted polyolefin elastomer with the mass ratio of 2:3), 3 parts of polyolefin elastomer, 1.5 parts of palm oil and 1.5 parts of color masterbatch as raw materials;
S2, mixing high-density polyethylene, functional additives, polyolefin elastomer, compatilizer, palm oil and color master batch, setting technological parameters of 10r/min of feeding rate, 35r/min of screw speed, and carrying out melt extrusion at 165 ℃, 170 ℃, 175 ℃, 185 ℃ and 175 ℃ in each temperature region, and setting technological parameters of 80bar of injection molding pressure and 200 ℃, 210 ℃, 215 ℃ and 220 ℃ in each temperature region, thus obtaining the high-strength polyethylene milk bottle cap.
Comparative example 2 based on example 1, a maleic anhydride-grafted polyolefin elastomer was singly used as a compatibilizer, the remainder being the same as example 1;
The preparation method comprises the steps of S1, adding 4 parts of polylysine into 3.2g/L nano montmorillonite dispersion liquid (containing 3.2 parts of nano montmorillonite and deionized water as solvent), conducting intercalation reaction for 2 hours at 65 ℃, centrifuging and drying to obtain modified nano montmorillonite, S2, adding 0.3 part of caffeic acid into 30 parts of PBS buffer solution under nitrogen atmosphere, adding 0.3 part of EDC and 0.18 part of NHS, stirring for 30 minutes under ice bath, adding modified nano montmorillonite-PBS buffer solution (1 part of modified nano montmorillonite and 30 parts of PBS buffer solution), continuing stirring for 24 hours, washing and drying to obtain the functional additive;
step 2, preparing a high-strength polyethylene milk bottle cap:
the preparation method comprises the steps of S1, (1) melting and extruding 9 parts of polyolefin elastomer, 1 part of 4-vinyl benzyl alcohol and 0.3 part of peroxidation initiator BPO in a double screw base, grinding components to obtain a hydroxylated modified polyolefin elastomer, (2) sequentially adding the hydroxylated modified polyolefin elastomer and a molybdenum catalyst in a mass ratio of 1:0.04 into DMF, reacting for 2 hours at 55 ℃, washing and drying to obtain the hydroformylation polyolefin elastomer;
s2, weighing 100 parts of high-density polyethylene, 6 parts of a functional additive, 3 parts of a maleic anhydride grafted polyolefin elastomer, 3 parts of an aldehyde polyolefin elastomer, 1.5 parts of palm oil and 1.5 parts of a color masterbatch as raw materials;
s3, (1) dispersing the functional additive and the aldehyde polyolefin elastomer in 100 parts of ethanol in turn, stirring and heating for 6 hours at 65 ℃, removing the solvent, and drying to obtain a raw material A;
(2) Mixing the raw material A with high-density polyethylene, maleic anhydride grafted polyolefin elastomer, palm oil and color master batch, setting the technological parameters of feeding rate of 10r/min, screw rotating speed of 35r/min, and carrying out melt extrusion at the temperatures of 165 ℃, 170 ℃, 175 ℃, 185 ℃ and 175 ℃ in each temperature region, wherein the technological parameters of injection molding at the injection pressure of 80bar are set, and the temperatures of 200 ℃, 210 ℃, 215 ℃ and 220 ℃ in each temperature region are set to obtain the high-strength polyethylene milk bottle cap.
Comparative example 3 based on example 1, the functional additive was caffeic acid modified nano montmorillonite, the remainder being the same as example 1;
Step 1, preparing a functional additive, namely adding 0.3 part of caffeic acid into 3.2g/L of nano montmorillonite dispersion liquid (containing 3.2 parts of nano montmorillonite and deionized water as a solvent), performing intercalation reaction for 2 hours at 65 ℃, centrifuging, and drying to obtain caffeic acid modified nano montmorillonite serving as the functional additive;
step 2, preparing a high-strength polyethylene milk bottle cap:
the preparation method comprises the steps of S1, (1) melting and extruding 9 parts of polyolefin elastomer, 1 part of 4-vinyl benzyl alcohol and 0.3 part of peroxidation initiator BPO in a double screw base, grinding components to obtain a hydroxylated modified polyolefin elastomer, (2) sequentially adding the hydroxylated modified polyolefin elastomer and a molybdenum catalyst in a mass ratio of 1:0.04 into DMF, reacting for 2 hours at 55 ℃, washing and drying to obtain the hydroformylation polyolefin elastomer;
s2, weighing 100 parts of high-density polyethylene, 6 parts of functional additive, 3 parts of compatilizer (maleic anhydride grafted polyethylene and maleic anhydride grafted polyolefin elastomer with the mass ratio of 2:3), 3 parts of aldehyde polyolefin elastomer, 1.5 parts of palm oil and 1.5 parts of color masterbatch as raw materials;
S3, mixing high-density polyethylene, functional additives, aldehyde polyolefin elastomer, compatilizer, palm oil and color master batch, setting technological parameters of 10r/min of feeding rate, 35r/min of screw speed, and carrying out melt extrusion at temperatures of 165 ℃, 170 ℃, 175 ℃, 185 ℃ and 175 ℃ in all temperature areas, and setting technological parameters of 80bar of injection molding pressure and carrying out injection molding at temperatures of 200 ℃, 210 ℃, 215 ℃ and 220 ℃ in all temperature areas to obtain the high-strength polyethylene milk bottle cap.
Comparative example 4 based on example 1, the amount of functional additive introduced was increased, the remainder being the same as example 1;
The preparation method comprises the steps of S1, adding 4 parts of polylysine into 3.2g/L nano montmorillonite dispersion liquid (containing 3.2 parts of nano montmorillonite and deionized water as solvent), conducting intercalation reaction for 2 hours at 65 ℃, centrifuging and drying to obtain modified nano montmorillonite, S2, adding 0.3 part of caffeic acid into 30 parts of PBS buffer solution under nitrogen atmosphere, adding 0.3 part of EDC and 0.18 part of NHS, stirring for 30 minutes under ice bath, adding modified nano montmorillonite-PBS buffer solution (1 part of modified nano montmorillonite and 30 parts of PBS buffer solution), continuing stirring for 24 hours, washing and drying to obtain the functional additive;
step 2, preparing a high-strength polyethylene milk bottle cap:
the preparation method comprises the steps of S1, (1) melting and extruding 9 parts of polyolefin elastomer, 1 part of 4-vinyl benzyl alcohol and 0.3 part of peroxidation initiator BPO in a double screw base, grinding components to obtain a hydroxylated modified polyolefin elastomer, (2) sequentially adding the hydroxylated modified polyolefin elastomer and a molybdenum catalyst in a mass ratio of 1:0.04 into DMF, reacting for 2 hours at 55 ℃, washing and drying to obtain the hydroformylation polyolefin elastomer;
s2, weighing 100 parts of high-density polyethylene, 10 parts of functional additive, 3 parts of compatilizer (maleic anhydride grafted polyethylene and maleic anhydride grafted polyolefin elastomer with the mass ratio of 2:3), 3 parts of aldehyde polyolefin elastomer, 1.5 parts of palm oil and 1.5 parts of color masterbatch as raw materials;
s3, (1) dispersing the functional additive and the aldehyde polyolefin elastomer in 100 parts of ethanol in turn, stirring and heating for 6 hours at 65 ℃, removing the solvent, and drying to obtain a raw material A;
(2) Mixing the raw material A with high-density polyethylene, a compatilizer, palm oil and a color master batch, setting the technological parameters of feeding rate of 10r/min, screw rotating speed of 35r/min, carrying out melt extrusion at the temperatures of 165 ℃, 170 ℃, 175 ℃, 185 ℃ and 175 ℃ in each temperature region, and setting the technological parameters of injection molding at the injection pressure of 80bar, and carrying out injection molding at the temperatures of 200 ℃,210 ℃, 215 ℃ and 220 ℃ in each temperature region to obtain the high-strength polyethylene milk bottle cap.
Performance test the high strength polyethylene milk bottle caps prepared in examples and comparative examples were subjected to a related performance test. The tensile strength was measured at a tensile rate of 200m/min (1) with reference to GB/T10004-2008, (2) the oxygen transmission rate was measured at 0.5 hour of pre-ventilation with reference to GB/T1038-2000, 3) the antioxidant (caffeic acid) migration test was performed by placing the bottle cap in 95% ethanol solution and treating at 70℃for 2 hours, and the migration amount was measured, and the data obtained are shown in the following table:
It is concluded from the data in the above table that the polyethylene milk bottle cap with high strength and high barrier property is obtained by the method, the data of comparative examples 1 to 4 are compared with those of example 1, namely that the interfacial effect and compatibility of the functional additive are reduced by using the polyolefin elastomer to replace the aldehyde polyolefin elastomer in comparative example 1, the mechanical property is reduced by using the single maleic anhydride grafted polyolefin elastomer as a compatilizer in comparative example 2, the interfacial effect and oxygen barrier property are reduced by using the caffeic acid modified nano montmorillonite as the functional additive in comparative example 3, and the mechanical property and barrier property are reduced by using too much introduction amount of the functional additive in comparative example 4.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and the present invention is not limited thereto, but may be modified or substituted for some of the technical features thereof by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2728187A1 (en) * | 2008-06-18 | 2009-12-23 | Lifebond Ltd | Improved cross-linked compositions |
| CN110016170A (en) * | 2018-01-10 | 2019-07-16 | 杭州福斯特应用材料股份有限公司 | A kind of low water vapor transmission rate polyolefin elastomer adhesive film and preparation method thereof |
| CN113121903A (en) * | 2021-04-12 | 2021-07-16 | 金富科技股份有限公司 | High-barrier plastic bottle cap and preparation method thereof |
| CN113372478A (en) * | 2021-06-24 | 2021-09-10 | 万华化学集团股份有限公司 | Aldehyde group functionalized cycloolefin-ethylene copolymer and preparation method thereof |
| CN114316378A (en) * | 2021-12-09 | 2022-04-12 | 浙江树人学院（浙江树人大学） | A kind of chitosan/ε-polylysine intercalated montmorillonite antibacterial packaging film and its preparation method and application |
-
2024
- 2024-09-29 CN CN202411367057.5A patent/CN119119614A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2728187A1 (en) * | 2008-06-18 | 2009-12-23 | Lifebond Ltd | Improved cross-linked compositions |
| CN110016170A (en) * | 2018-01-10 | 2019-07-16 | 杭州福斯特应用材料股份有限公司 | A kind of low water vapor transmission rate polyolefin elastomer adhesive film and preparation method thereof |
| CN113121903A (en) * | 2021-04-12 | 2021-07-16 | 金富科技股份有限公司 | High-barrier plastic bottle cap and preparation method thereof |
| CN113372478A (en) * | 2021-06-24 | 2021-09-10 | 万华化学集团股份有限公司 | Aldehyde group functionalized cycloolefin-ethylene copolymer and preparation method thereof |
| CN114316378A (en) * | 2021-12-09 | 2022-04-12 | 浙江树人学院（浙江树人大学） | A kind of chitosan/ε-polylysine intercalated montmorillonite antibacterial packaging film and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| 吕夏燕;: "聚乙烯/蒙脱土复合材料的制备及阻隔性能研究", 农村经济与科技, no. 22, 30 November 2016 (2016-11-30) * |
| 王文广: "《塑料改性实用技术》", vol. 1, 31 March 2000, 中国轻工业出版社, pages: 452 * |
| 邢玉清编译: "《简明塑料大全》", vol. 1, 30 September 2002, 哈尔滨工业大学出版社, pages: 430 * |
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