High-performance polypropylene derivative for packaging material and preparation method of high-performance polypropylene derivative

Abstract

The invention discloses a high-performance polypropylene derivative for a packaging material and a preparation method of the high-performance polypropylene derivative, and relates to the technical field of plastics. The high-performance polypropylene derivative for the packaging material prepared by the invention comprises a modified polypropylene base material, a cycloolefin copolymer, a nucleating agent and intercalated montmorillonite, the modified polypropylene resin base material is prepared by melt blending of polypropylene and polyamide siloxane; polypropylene and a polymer with amide and siloxane are subjected to melt blending, so that the toughness and the antistatic property are improved while the scraping property is ensured. The intercalated montmorillonite is prepared from an acrylate polymer and montmorillonite through a reaction, the acrylate polymer is prepared from N-vinyl pyrrolidone and perfluoroepoxy methacrylate through a reaction, and the perfluoroepoxy methacrylate is acyl fluoride functionalized hexafluoropropylene oxide prepared through ring opening oligomerization of hexafluoropropylene oxide; according to the present invention, the toughness is improved, and the barrier property of the polypropylene derivative is enhanced at the same time.

Description

Technical Field

[0001] This invention relates to the field of plastics technology, specifically to a high-performance polypropylene derivative for packaging materials and its preparation method. Background Technology

[0002] In today's era of simultaneous consumption upgrades and environmental protection requirements, traditional polypropylene packaging materials can no longer meet the demands of the food and pharmaceutical industries for high performance and high safety. Therefore, high-performance polypropylene derivatives, such as metallocene polypropylene, high-crystallinity polypropylene, high melt strength polypropylene, and polyolefin elastomers, have emerged. Through molecular structure design and multi-component compounding, they achieve synergistic optimization of strength, toughness, barrier properties, optical properties, and processability, becoming a crucial support for the packaging industry's transformation towards high-end and functional products.

[0003] High-performance polypropylene derivatives, through continuous molecular structure innovation and composite modification, provide the packaging industry with material solutions that combine excellent performance, exquisite appearance, and environmental friendliness. While enhancing the value of packaging, they also contribute significantly to resource conservation and environmental friendliness. Therefore, this invention studies and prepares a high-performance polypropylene derivative for packaging materials with high toughness and barrier properties. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a high-performance polypropylene derivative for packaging materials and a method for preparing the same.

[0005] The present invention proposes a technical solution to solve the above-mentioned technical problems as follows: a high-performance polypropylene derivative for packaging materials, comprising modified polypropylene base material, antioxidant and intercalated montmorillonite; wherein the modified polypropylene resin base material is obtained by melt blending polypropylene and polyamide-based siloxane; and the intercalated montmorillonite is obtained by reacting acrylate polymer with montmorillonite.

[0006] Preferably, the polyamide-based siloxane is prepared by reacting polyethylene 2,5-furan dicarboxylate with isocyanate siloxane; the isocyanate siloxane is prepared by reacting 4,4'-diphenylmethane diisocyanate with hydroxyl-terminated polydimethylsiloxane.

[0007] Preferably, the acrylate polymer is prepared by reacting N-vinylpyrrolidone with perfluoroepoxy methacrylate; the perfluoroepoxy methacrylate is prepared by ring-opening oligomerization of hexafluoroepoxypropane to obtain fluorine-functionalized hexafluoroepoxypropane, followed by hydrolysis and esterification with methacryloxy chloride.

[0008] Preferably, the antioxidant is antioxidant 1010.

[0009] Preferably, the method for preparing a high-performance polypropylene derivative for packaging materials includes the following specific steps: S1. Under a nitrogen atmosphere, polyethylene 2,5-furandicarboxylate and N,N-dimethylformamide are mixed at a mass ratio of 1:2~3, heated to 60~70℃, stirred and dissolved, then cooled to 40~45℃, and dibutyltin dilaurate catalyst (0.01~0.03 times the mass of polyethylene 2,5-furandicarboxylate) is added. After stirring evenly, isocyanate siloxane (1.8~2.2 times the mass of polyethylene 2,5-furandicarboxylate) is added, heated to 50~55℃, and stirred at 100~200 rpm for 4~6 h. After cooling to room temperature, polyamide-based siloxane is obtained. S2. Polypropylene and polyamide-based siloxane are mixed at a mass ratio of 40~60:1, placed in a high-speed mixer, and mixed at 70~90℃ and 900~1200rpm for 8~10min. The mixture is then transferred to a twin-screw extruder and melt-extruded and granulated at 180~190℃ to obtain a modified polypropylene resin base material. S3. A mixture of fluorine-functionalized hexafluoropropylene oxide, methanol, diethyl ether, sodium carbonate, and magnesium sulfate in a mass ratio of 0.2-0.4:1-2:20-50:0.01:0.01 was prepared and reacted at room temperature for 14-16 hours. Then, sodium borohydride (0.5-0.7 times the mass of the fluorine-functionalized hexafluoropropylene oxide) and methanol (8-10 times the mass of the fluorine-functionalized hexafluoropropylene oxide) were added and the mixture was refluxed for 14-16 hours. The mixture was quenched with hydrochloric acid, washed successively with deionized water and saturated sodium chloride solution, cooled to 0-2°C, and then methacryloyl chloride, triethylamine, and tetrahydrofuran were added. The mixture was heated to room temperature and reacted for 8-12 hours. The mixture was washed successively with deionized water and saturated sodium bicarbonate solution, dried with magnesium sulfate, and distilled under reduced pressure to obtain perfluoroepoxy methacrylate. S4. Mix the acrylate polymer with N,N-dimethylformamide at a mass ratio of 6~7:1, stir to dissolve, add 0.001~0.003 times the mass of the acrylate polymer as a catalyst dibutyltin dilaurate, stir evenly, add 0.06~0.08 times the mass of the acrylate polymer as pretreated montmorillonite, react for 20~30 min, raise the temperature to 70~80℃, continue the reaction for 4~6 h, cool to 50~60℃, degas under vacuum to obtain intercalated montmorillonite; S5. Mix the modified polypropylene base material, antioxidant and intercalated montmorillonite, place in a high-speed mixer, mix at 70~90℃ and 900~1200rpm for 8~10min, transfer to a twin-screw extruder, melt extrude and granulate at 180~190℃ to obtain a high-performance polypropylene derivative for packaging materials.

[0010] Preferably, in step S1 above, the method for preparing isocyanate siloxane is as follows: under a nitrogen atmosphere, hydroxyl-terminated polydimethylsiloxane and N,N-dimethylformamide are mixed at a mass ratio of 5:3~4, stirred evenly, and then 0.001~0.003 times the mass of the hydroxyl-terminated polydimethylsiloxane catalyst dibutyltin dilaurate is added. A 30~60% N,N-dimethylformamide solution of 4,4'-diphenylmethane diisocyanate is added dropwise at a rate of 1~3 ml / min. The reaction is continued at 35~40℃ for 5~7 h, and then cooled to room temperature to obtain isocyanate siloxane.

[0011] Preferably, in step S1 above, the method for preparing isocyanate siloxane is as follows: under a nitrogen atmosphere, hydroxyl-terminated polydimethylsiloxane and N,N-dimethylformamide are mixed at a mass ratio of 5:3~4, stirred evenly, and then 0.001~0.003 times the mass of the hydroxyl-terminated polydimethylsiloxane catalyst dibutyltin dilaurate is added. A 30~60% N,N-dimethylformamide solution of 4,4'-diphenylmethane diisocyanate is added dropwise at a rate of 1~3 ml / min. The reaction is continued at 35~40℃ for 5~7 h, and then cooled to room temperature to obtain isocyanate siloxane.

[0012] Preferably, in step S3 above, the mass ratio of fluorinated hexafluoropropylene oxide, methacryloyl chloride, triethylamine, and tetrahydrofuran is 1:2~4:3~5:40.

[0013] Preferably, in step S4 above, the method for preparing pretreated montmorillonite is as follows: under a nitrogen atmosphere, montmorillonite, diphenylmethane diisocyanate and toluene are mixed at a mass ratio of 1:0.3~0.5:200, heated to 80~85℃, reacted for 8~10h, filtered and washed with toluene, and finally dried at 100~110℃ to obtain pretreated montmorillonite.

[0014] Preferably, in step S5 above, the mass ratio of modified polypropylene base material, antioxidant and intercalated montmorillonite is 50~60:0.2~0.3:10~20.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: The high-performance polypropylene derivative for packaging materials prepared by this invention includes modified polypropylene base material, cyclic olefin copolymer, nucleating agent and intercalated montmorillonite; The modified polypropylene resin base is obtained by melt blending polypropylene and polyamide-based siloxane. The polyamide-based siloxane is obtained by reacting polyethylene 2,5-furan dicarboxylate with isocyanate siloxane, and the isocyanate siloxane is obtained by reacting 4,4'-diphenylmethane diisocyanate with hydroxyl-terminated polydimethylsiloxane. Mel-blending polypropylene with polymers containing amides and siloxanes improves toughness and antistatic properties while ensuring scratch resistance.

[0016] Intercalated montmorillonite is prepared by reacting acrylate polymers with montmorillonite. The acrylate polymers are prepared by reacting N-vinylpyrrolidone with perfluoroepoxy methacrylate. The perfluoroepoxy methacrylate is prepared by ring-opening oligomerization of hexafluoroepoxypropane to obtain fluorine-functionalized hexafluoroepoxypropane, which is then hydrolyzed and esterified with methacryloyl chloride. The acrylate-intercalated montmorillonite has a larger spacing, which not only makes the polypropylene derivative more dispersed and further improves its toughness, but also enhances the barrier properties of the polypropylene derivative by forming a "zigzag path". Detailed Implementation

[0017] The present invention will be specifically described below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those skilled in the art.

[0018] To more clearly illustrate the method provided by the present invention, the following examples will be used to describe in detail the testing methods for various indicators of the packaging materials prepared in the examples and comparative examples using high-performance polypropylene derivatives: Toughness: The packaging materials prepared in the examples and comparative examples were subjected to impact strength tests using high-performance polypropylene derivatives in accordance with GB / T1043.1.

[0019] Antistatic properties: The surface resistivity of the packaging materials prepared in the examples and comparative examples was tested using high-performance polypropylene derivatives in accordance with GB / T31838.3.

[0020] Barrier properties: The packaging materials prepared in the examples and comparative examples were tested for oxygen permeability using high-performance polypropylene derivatives in accordance with GB / T1038.

[0021] Example 1 The preparation method of the high-performance polypropylene derivative for packaging materials in this embodiment is as follows: S1. Under a nitrogen atmosphere, hydroxyl-terminated polydimethylsiloxane and N,N-dimethylformamide were mixed at a mass ratio of 5:3 and stirred until homogeneous. Then, dibutyltin dilaurate catalyst (0.001 times the mass of the hydroxyl-terminated polydimethylsiloxane) was added. A 30% (w / min) solution of 4,4'-diphenylmethane diisocyanate in N,N-dimethylformamide was added dropwise. The reaction was continued at 35°C for 5 hours, and then cooled to room temperature to obtain isocyanate siloxane. Under a nitrogen atmosphere, ... Poly(2,5-furandicarboxylate) and N,N-dimethylformamide were mixed at a mass ratio of 1:2, heated to 60°C, stirred and dissolved, then cooled to 40°C. Dibutyltin dilaurate catalyst (0.01 times the mass of poly(2,5-furandicarboxylate)) was added and stirred until homogeneous. Isocyanate siloxane (1.8 times the mass of poly(2,5-furandicarboxylate)) was then added. The mixture was heated to 50°C and stirred at 100 rpm for 4 hours. After cooling to room temperature, polyamide-based siloxane was obtained. S2. Polypropylene and polyamide-based siloxane are mixed at a mass ratio of 40:1, placed in a high-speed mixer, mixed at 70°C and 900 rpm for 8 minutes, transferred to a twin-screw extruder, and melt-extruded and granulated at 180°C to obtain modified polypropylene resin base material. S3. Under a nitrogen atmosphere, cesium fluoride and tetraethylene glycol dimethyl ether were mixed at a mass ratio of 0.1:3, cooled to 0°C, and hexafluoropropylene oxide (40 times the mass of cesium fluoride) was added dropwise at a rate of 1 ml / min. The mixture was heated to 100°C and reacted for 6 h. After cooling to room temperature, the mixture was distilled under reduced pressure to obtain acyl fluoride-functionalized hexafluoropropylene oxide. Acyl fluoride-functionalized hexafluoropropylene oxide, methanol, diethyl ether, sodium carbonate, and magnesium sulfate were mixed at a mass ratio of 0.2:1:20:0.01:0.01 and reacted at room temperature for 14 h. Then, the mass of acyl fluoride-functionalized hexafluoropropylene oxide was added. 0.5 times the mass of sodium borohydride and 8 times the mass of methanol of fluorinated hexafluoropropylene oxide were refluxed for 14 h. The mixture was quenched with hydrochloric acid, washed successively with deionized water and saturated sodium chloride solution, cooled to 0 °C, and then methacryloyl chloride, triethylamine and tetrahydrofuran were added. The mass ratio of fluorinated hexafluoropropylene oxide, methacryloyl chloride, triethylamine and tetrahydrofuran was 1:2:3:40. The mixture was heated to room temperature and reacted for 8 h. The mixture was washed successively with deionized water and saturated sodium bicarbonate solution, dried with magnesium sulfate, and distilled under reduced pressure to obtain perfluoroepoxy methacrylate. S4. Under a nitrogen atmosphere, montmorillonite, diphenylmethane diisocyanate, and toluene were mixed at a mass ratio of 1:0.3:200, heated to 80°C, and reacted for 8 hours. The mixture was then filtered and washed with toluene, and finally dried at 100°C to obtain pretreated montmorillonite. Acrylic polymer and N,N-dimethylformamide were mixed at a mass ratio of 6:1, stirred and dissolved, and then 0.001 times the mass of the acrylate polymer catalyst, dibutyltin dilaurate, was added. After stirring evenly, 0.06 times the mass of the acrylate polymer pretreated montmorillonite was added. After reacting for 20 minutes, the temperature was raised to 70°C and the reaction continued for 4 hours. The temperature was then lowered to 50°C, and the mixture was degassed under vacuum to obtain intercalated montmorillonite. S5. The modified polypropylene base material, antioxidant and intercalated montmorillonite are mixed at a mass ratio of 50:0.2:10, placed in a high-speed mixer, and mixed at 70°C and 900 rpm for 8 min. The mixture is then transferred to a twin-screw extruder and melt-extruded and granulated at 180°C to obtain a high-performance polypropylene derivative for packaging materials.

[0022] Example 2 The preparation method of the high-performance polypropylene derivative for packaging materials in this embodiment is as follows: S1. Under a nitrogen atmosphere, hydroxyl-terminated polydimethylsiloxane and N,N-dimethylformamide were mixed at a mass ratio of 5:3.5 and stirred until homogeneous. Then, dibutyltin dilaurate catalyst (0.002 times the mass of the hydroxyl-terminated polydimethylsiloxane) was added. A 45% (w / w) solution of 4,4'-diphenylmethane diisocyanate in N,N-dimethylformamide was added dropwise at a rate of 2 ml / min. The reaction was continued at 38 °C for 6 h, and then cooled to room temperature to obtain isocyanate siloxane. Under a nitrogen atmosphere, Poly(2,5-furandicarboxylate) and N,N-dimethylformamide were mixed at a mass ratio of 1:2.5, heated to 5°C, stirred and dissolved, then cooled to 43°C. Dibutyltin dilaurate catalyst (0.012 times the mass of poly(2,5-furandicarboxylate)) was added and stirred until homogeneous. Then, isocyanate siloxane (2.0 times the mass of poly(2,5-furandicarboxylate)) was added, heated to 53°C, and stirred at 150 rpm for 5 hours. The mixture was then cooled to room temperature to obtain polyamide-based siloxane. S2. Polypropylene and polyamide-based siloxane are mixed at a mass ratio of 50:1, placed in a high-speed mixer, mixed at 80°C and 1100 rpm for 9 minutes, transferred to a twin-screw extruder, and melt-extruded and granulated at 185°C to obtain modified polypropylene resin base material. S3. Under a nitrogen atmosphere, cesium fluoride and tetraethylene glycol dimethyl ether were mixed at a mass ratio of 0.11:3, cooled to 1°C, and hexafluoropropylene oxide (45 times the mass of cesium fluoride) was added dropwise at a rate of 2 ml / min. The mixture was heated to 110°C and reacted for 9 h. After cooling to room temperature, the mixture was distilled under reduced pressure to obtain acyl fluoride-functionalized hexafluoropropylene oxide. Acyl fluoride-functionalized hexafluoropropylene oxide, methanol, diethyl ether, sodium carbonate, and magnesium sulfate were mixed at a mass ratio of 0.3:3:35:0.01:0.01 and reacted at room temperature for 5 h. Then, the mass of acyl fluoride-functionalized hexafluoropropylene oxide was added. Sodium borohydride (0.6 times its mass) and methanol (9 times its mass) of fluorinated hexafluoropropylene oxide were refluxed for 15 h. The mixture was quenched with hydrochloric acid, washed successively with deionized water and saturated sodium chloride solution, cooled to 1 °C, and then methacryloyl chloride, triethylamine, and tetrahydrofuran were added. The mass ratio of fluorinated hexafluoropropylene oxide, methacryloyl chloride, triethylamine, and tetrahydrofuran was 1:3:4:40. The mixture was heated to room temperature and reacted for 10 h. The mixture was washed successively with deionized water and saturated sodium bicarbonate solution, dried over magnesium sulfate, and distilled under reduced pressure to obtain perfluoroepoxy methacrylate. S4. Under a nitrogen atmosphere, montmorillonite, diphenylmethane diisocyanate, and toluene were mixed at a mass ratio of 1:0.4:200, heated to 83°C, and reacted for 9 hours. The mixture was then filtered and washed with toluene, and finally dried at 105°C to obtain pretreated montmorillonite. An acrylate polymer and N,N-dimethylformamide were mixed at a mass ratio of 6.5:1, stirred until dissolved, and then 0.002 times the mass of the acrylate polymer catalyst, dibutyltin dilaurate, was added. After stirring until homogeneous, 0.07 times the mass of the acrylate polymer pretreated montmorillonite was added. The mixture was reacted for 25 minutes, then heated to 75°C and reacted for another 5 hours. The mixture was then cooled to 55°C and degassed under vacuum to obtain intercalated montmorillonite. S5. The modified polypropylene base material, antioxidant and intercalated montmorillonite are mixed at a mass ratio of 55:0.25:15, placed in a high-speed mixer, and mixed at 80℃ and 1100rpm for 9min. The mixture is then transferred to a twin-screw extruder and melt-extruded and granulated at 185℃ to obtain a high-performance polypropylene derivative for packaging materials.

[0023] Example 3 The preparation method of the high-performance polypropylene derivative for packaging materials in this embodiment is as follows: S1. Under a nitrogen atmosphere, hydroxyl-terminated polydimethylsiloxane and N,N-dimethylformamide were mixed at a mass ratio of 5:4 and stirred until homogeneous. Then, dibutyltin dilaurate catalyst (0.003 times the mass of the hydroxyl-terminated polydimethylsiloxane) was added. A 60% (w / w) solution of 4,4'-diphenylmethane diisocyanate in N,N-dimethylformamide was added dropwise at a rate of 3 ml / min. The reaction was continued at 40 °C for 7 h, and then cooled to room temperature to obtain isocyanate siloxane. Under a nitrogen atmosphere, ... Poly(2,5-furandicarboxylate) and N,N-dimethylformamide were mixed at a mass ratio of 1:3, heated to 70°C, stirred and dissolved, then cooled to 45°C, and 0.03 times the mass of poly(2,5-furandicarboxylate) catalyst dibutyltin dilaurate was added. After stirring evenly, 2.2 times the mass of poly(2,5-furandicarboxylate) isocyanate siloxane was added, heated to 55°C, stirred at 200 rpm for 6 hours, and cooled to room temperature to obtain polyamide-based siloxane. S2. Polypropylene and polyamide-based siloxane are mixed at a mass ratio of 60:1, placed in a high-speed mixer, and mixed at 90°C and 1200 rpm for 10 minutes. The mixture is then transferred to a twin-screw extruder and melt-extruded and granulated at 190°C to obtain a modified polypropylene resin base material. S3. Under a nitrogen atmosphere, cesium fluoride and tetraethylene glycol dimethyl ether were mixed at a mass ratio of 0.12:3, cooled to 2°C, and hexafluoropropylene oxide (50 times the mass of cesium fluoride) was added dropwise at a rate of 3 ml / min. The mixture was heated to 120°C and reacted for 12 h. After cooling to room temperature, the mixture was distilled under reduced pressure to obtain acyl fluoride-functionalized hexafluoropropylene oxide. Acyl fluoride-functionalized hexafluoropropylene oxide, methanol, diethyl ether, sodium carbonate, and magnesium sulfate were mixed at a mass ratio of 0.4:2:50:0.01:0.01 and reacted at room temperature for 16 h. Then, the mass of acyl fluoride-functionalized hexafluoropropylene oxide was added. 0.7 times the mass of sodium borohydride and 10 times the mass of methanol of fluorinated hexafluoropropylene oxide were refluxed for 16 h. The mixture was quenched with hydrochloric acid, washed successively with deionized water and saturated sodium chloride solution, cooled to 2 °C, and then methacryloyl chloride, triethylamine and tetrahydrofuran were added. The mass ratio of fluorinated hexafluoropropylene oxide, methacryloyl chloride, triethylamine and tetrahydrofuran was 1:4:5:40. The mixture was heated to room temperature and reacted for 12 h. The mixture was washed successively with deionized water and saturated sodium bicarbonate solution, dried with magnesium sulfate, and distilled under reduced pressure to obtain perfluoroepoxy methacrylate. S4. Under a nitrogen atmosphere, montmorillonite, diphenylmethane diisocyanate, and toluene were mixed at a mass ratio of 1:0.5:200, heated to 85°C, and reacted for 10 hours. The mixture was then filtered and washed with toluene, and finally dried at 110°C to obtain pretreated montmorillonite. An acrylate polymer and N,N-dimethylformamide were mixed at a mass ratio of 7:1, stirred until dissolved, and then 0.003 times the mass of the acrylate polymer catalyst, dibutyltin dilaurate, was added. After stirring until homogeneous, 0.08 times the mass of the acrylate polymer pretreated montmorillonite was added. The mixture was reacted for 30 minutes, then heated to 80°C and reacted for another 6 hours. The mixture was then cooled to 60°C and degassed under vacuum to obtain intercalated montmorillonite. S5. The modified polypropylene base material, antioxidant and intercalated montmorillonite are mixed at a mass ratio of 60:0.3:20 and placed in a high-speed mixer. The mixture is mixed at 90°C and 1200 rpm for 10 min. The mixture is then transferred to a twin-screw extruder and melt-extruded and granulated at 190°C to obtain a high-performance polypropylene derivative for packaging materials.

[0024] Comparative Example 1 The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between this packaging material and Example 2 is that the high-performance polypropylene derivative is used, and the difference is that the polyamide-based siloxane is prepared by reacting polyethylene 2,5-furan dicarboxylate with hydroxyl-terminated polydimethylsiloxane.

[0025] Comparative Example 2 The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between this packaging material and Example 2 is that the modified polypropylene resin base is prepared by melt blending polypropylene with hydroxyl-terminated polydimethylsiloxane.

[0026] Comparative Example 3 The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between this packaging material and Example 2 is that it only includes polypropylene, cyclic olefin copolymer, nucleating agent and intercalated montmorillonite.

[0027] Comparative Example 4 The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between this packaging material, which uses a high-performance polypropylene derivative, and Example 2 is that the intercalated montmorillonite is prepared by reacting perfluoroepoxy methacrylate with montmorillonite.

[0028] Comparative Example 5 The preparation method of Comparative Example 5 is the same as that of Example 2. The difference between this packaging material and Example 2 is that it uses a high-performance polypropylene derivative, which includes a modified polypropylene base, a cyclic olefin copolymer, a nucleating agent, and montmorillonite.

[0029] Comparative Example 6 The preparation method of Comparative Example 6 is the same as that of Example 2. The difference between this packaging material and Example 2 is that it uses a high-performance polypropylene derivative, which includes a modified polypropylene base material, a cyclic olefin copolymer, and a nucleating agent.

[0030] Example of effect Table 1 below shows the performance test results of the high-performance polypropylene derivatives for packaging materials prepared in the examples and comparative examples; Table 1 Impact strength (kJ / m²) Surface resistivity (Ω) <![CDATA[Oxygen transmission rate (cm 3 / cm 2 ·24 h·atm)]]> Example 1 49 <![CDATA[1.5×10 13 ]]> 1.054 Example 2 52 <![CDATA[4.5×10 13 ]]> 0.991 Example 3 50 <![CDATA[8.4×10 13 ]]> 1.103 Comparative Example 1 40 <![CDATA[3.1×10 9 ]]> 1.268 Comparative Example 2 37 <![CDATA[7.4×10 9 ]]> 1.257 Comparative Example 3 34 <![CDATA[2.8×10 8 ]]> 1.296 Comparative Example 4 36 <![CDATA[4.2×10 13 ]]> 3.276 Comparative Example 5 33 <![CDATA[5.6×10 13 ]]> 3.681 Comparative Example 6 31 <![CDATA[3.2×10 13 ]]> 3.953 As can be seen from the performance data comparison in Table 1, the high-performance polypropylene derivative for packaging materials prepared by this invention has excellent tear resistance and mechanical properties.

[0031] Comparison of experimental data from Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 reveals that the modified polypropylene resin base material is obtained by melt blending polypropylene with polyamide-based siloxane. The polyamide-based siloxane is obtained by reacting polyethylene 2,5-furan dicarboxylate with isocyanate siloxane, and the isocyanate siloxane is obtained by reacting 4,4'-diphenylmethane diisocyanate with hydroxyl-terminated polydimethylsiloxane. Mel-blending polypropylene with polymers containing amides and siloxanes improves toughness and antistatic properties while ensuring scratch resistance.

[0032] Comparison of experimental data from Examples 1, 2, 3 and Comparative Examples 4, 5, and 6 reveals that intercalated montmorillonite is prepared by reacting acrylate polymers with montmorillonite. The acrylate polymers are prepared by reacting N-vinylpyrrolidone with perfluoroepoxy methacrylate. The perfluoroepoxy methacrylate is prepared by ring-opening oligomerization of hexafluoroepoxypropane to obtain fluorine-functionalized hexafluoroepoxypropane, followed by hydrolysis and esterification with methacryloyl chloride. The acrylate-intercalated montmorillonite has a larger spacing, which not only makes the polypropylene derivative more dispersed and further improves its toughness, but also enhances the barrier properties of the polypropylene derivative by forming a "zigzag path".

[0033] Obviously, the above embodiments are merely examples to clearly illustrate the embodiments of the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all embodiments here. However, these obvious variations or modifications derived from the spirit of the present invention are still within the protection scope of the present invention.

Claims

1. A high-performance polypropylene derivative for packaging materials, characterized in that, It includes a modified polypropylene base material, an antioxidant, and intercalated montmorillonite; the modified polypropylene resin base material is obtained by melt blending polypropylene and polyamide-based siloxane; the intercalated montmorillonite is obtained by reacting acrylate polymer with montmorillonite.

2. The high-performance polypropylene derivative for packaging materials according to claim 1, characterized in that, The polyamide-based siloxane is prepared by reacting polyethylene 2,5-furan dicarboxylate with isocyanate siloxane; the isocyanate siloxane is prepared by reacting 4,4'-diphenylmethane diisocyanate with hydroxyl-terminated polydimethylsiloxane.

3. The high-performance polypropylene derivative for packaging materials according to claim 1, characterized in that, The acrylate polymer is prepared by reacting N-vinylpyrrolidone with perfluoroepoxy methacrylate; the perfluoroepoxy methacrylate is prepared by ring-opening oligomerization of hexafluoroepoxypropane to obtain fluorine-functionalized hexafluoroepoxypropane, followed by hydrolysis and esterification with methacryloyl chloride.

4. The high-performance polypropylene derivative for packaging materials according to claim 1, characterized in that, The antioxidant is antioxidant 1010.

5. The method for preparing a high-performance polypropylene derivative for packaging materials according to claim 1, characterized in that, The specific steps include the following: S1. Under a nitrogen atmosphere, polyethylene 2,5-furandicarboxylate and N,N-dimethylformamide are mixed at a mass ratio of 1:2~3, heated to 60~70℃, stirred and dissolved, then cooled to 40~45℃, and dibutyltin dilaurate catalyst (0.01~0.03 times the mass of polyethylene 2,5-furandicarboxylate) is added. After stirring evenly, isocyanate siloxane (1.8~2.2 times the mass of polyethylene 2,5-furandicarboxylate) is added, heated to 50~55℃, and stirred at 100~200 rpm for 4~6 h. After cooling to room temperature, polyamide-based siloxane is obtained. S2. Polypropylene and polyamide-based siloxane are mixed at a mass ratio of 40~60:1, placed in a high-speed mixer, and mixed at 70~90℃ and 900~1200rpm for 8~10min. The mixture is then transferred to a twin-screw extruder and melt-extruded and granulated at 180~190℃ to obtain a modified polypropylene resin base material. S3. A mixture of fluorine-functionalized hexafluoropropylene oxide, methanol, diethyl ether, sodium carbonate, and magnesium sulfate in a mass ratio of 0.2-0.4:1-2:20-50:0.01:0.01 was prepared and reacted at room temperature for 14-16 hours. Then, sodium borohydride (0.5-0.7 times the mass of the fluorine-functionalized hexafluoropropylene oxide) and methanol (8-10 times the mass of the fluorine-functionalized hexafluoropropylene oxide) were added and the mixture was refluxed for 14-16 hours. The mixture was quenched with hydrochloric acid, washed successively with deionized water and saturated sodium chloride solution, cooled to 0-2°C, and then methacryloyl chloride, triethylamine, and tetrahydrofuran were added. The mixture was heated to room temperature and reacted for 8-12 hours. The mixture was washed successively with deionized water and saturated sodium bicarbonate solution, dried with magnesium sulfate, and distilled under reduced pressure to obtain perfluoroepoxy methacrylate. S4. Mix the acrylate polymer with N,N-dimethylformamide at a mass ratio of 6~7:1, stir to dissolve, add 0.001~0.003 times the mass of the acrylate polymer as a catalyst dibutyltin dilaurate, stir evenly, add 0.06~0.08 times the mass of the acrylate polymer as pretreated montmorillonite, react for 20~30 min, raise the temperature to 70~80℃, continue the reaction for 4~6 h, cool to 50~60℃, degas under vacuum to obtain intercalated montmorillonite; S5. Mix the modified polypropylene base material, antioxidant and intercalated montmorillonite, place in a high-speed mixer, mix at 70~90℃ and 900~1200rpm for 8~10min, transfer to a twin-screw extruder, melt extrude and granulate at 180~190℃ to obtain a high-performance polypropylene derivative for packaging materials.

6. The method for preparing a high-performance polypropylene derivative for packaging materials according to claim 5, characterized in that, In step S1 above, the method for preparing isocyanate siloxane is as follows: Under a nitrogen atmosphere, hydroxyl-terminated polydimethylsiloxane and N,N-dimethylformamide are mixed at a mass ratio of 5:3~4. After stirring evenly, 0.001~0.003 times the mass of the hydroxyl-terminated polydimethylsiloxane catalyst dibutyltin dilaurate is added. A 30~60% N,N-dimethylformamide solution of 4,4'-diphenylmethane diisocyanate is added dropwise at a rate of 1~3 ml / min. The reaction is continued at 35~40℃ for 5~7 h. After cooling to room temperature, isocyanate siloxane is obtained.

7. The method for preparing a high-performance polypropylene derivative for packaging materials according to claim 5, characterized in that, In step S3 above, the preparation method of acyl fluoride-functionalized hexafluoropropylene oxide is as follows: under a nitrogen atmosphere, cesium fluoride and tetraethylene glycol dimethyl ether are mixed at a mass ratio of 0.1~0.12:3, cooled to 0~2℃, and hexafluoropropylene oxide with a mass of 40~50 times that of cesium fluoride is added dropwise at a rate of 1~3 ml / min. The temperature is raised to 100~120℃, the reaction is carried out for 6~12 h, cooled to room temperature and distilled under reduced pressure to obtain acyl fluoride-functionalized hexafluoropropylene oxide.

8. The method for preparing a high-performance polypropylene derivative for packaging materials according to claim 5, characterized in that, In step S3 above, the mass ratio of acyl fluoride-functionalized hexafluoropropylene oxide, methacryloyl chloride, triethylamine, and tetrahydrofuran is 1:2~4:3~5:

40.

9. The method for preparing a high-performance polypropylene derivative for packaging materials according to claim 5, characterized in that, In step S4 above, the pretreated montmorillonite is prepared by mixing montmorillonite, diphenylmethane diisocyanate and toluene in a mass ratio of 1:0.3~0.5:200 under a nitrogen atmosphere, heating to 80~85℃, reacting for 8~10h, filtering and washing with toluene, and finally drying at 100~110℃ to obtain pretreated montmorillonite.

10. The method for preparing a high-performance polypropylene derivative for packaging materials according to claim 5, characterized in that, In step S5 above, the mass ratio of modified polypropylene base material, antioxidant and intercalated montmorillonite is 50~60:0.2~0.3:10~20.