Preparation method of zeolite modified polypropylene material

Abstract

The invention provides a preparation method of a zeolite modified polypropylene material. The preparation method comprises the following steps: (1) roasting zeolite powder; (2) preparing sodium dodecyl benzene sulfonate modified zeolite; mixing the sodium dodecyl benzene sulfonate modified zeolite with citric acid and deionized water to prepare carboxylated zeolite; (3) preparing polyhedral oligomeric silsesquioxane modified zeolite from an organic solvent, the carboxylated zeolite, amino polyhedral oligomeric silsesquioxane,-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide; and (4) mixing polypropylene, maleic anhydride grafted polypropylene, polyhedral oligomeric silsesquioxane modified zeolite and an antioxidant to obtain a mixture, and then putting the mixture into a twin-screw extruder for melt blending, extrusion and granulation. The zeolite modified polypropylene material prepared by the method disclosed by the invention has higher tensile strength and impact strength, so that the zeolite modified polypropylene material has a very good application effect in the field of plastic flowerpots.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a method for preparing a zeolite-modified polypropylene material. Background Art

[0002] Flower pots are utensils for planting flowers and are indispensable items in gardening and home decoration. Flower pots are made of various materials, including ceramic flower pots, plastic flower pots, metal flower pots, glass flower pots, etc. Among them, plastic flower pots have certain toughness and are not easy to break. They can withstand collisions and falls in daily use. At the same time, they have the advantages of being light in weight and affordable, making the application of plastics in the field of gardening more and more extensive. Polypropylene is often used to prepare plastic flower pots because of its good toughness, rigidity and corrosion resistance.

[0003] However, a flower pot with good performance needs to not only provide sufficient growth space for flowers and plants, but also have good air permeability. However, the air permeability of flower pots made directly from polypropylene is poor, which will affect the growth of flowers and plants. Therefore, it is necessary to modify polypropylene to enhance its air permeability.

[0004] At present, in order to enhance the air permeability of polypropylene plastic products, a large amount of zeolite is often used to fill and modify them. Zeolite is a silicate with silicon-oxygen tetrahedron and aluminum-oxygen tetrahedron as the skeleton. Its skeleton structure contains a large number of uniform cavities and pores inside it, and the electronegativity generated by the silicon-oxygen and aluminum-oxygen structures and the large specific surface area generated by the large number of microporous structures give zeolite a high ion adsorption capacity and ion exchange capacity. However, since zeolite is a hydrophilic material and polypropylene is a lipophilic material, the compatibility of the two is poor. Although a large amount of zeolite is compounded with polypropylene, the air permeability of the polypropylene material is enhanced, but the impact resistance of the resulting polypropylene composite material is reduced, so that the polypropylene plastic flower pot is easily damaged by external forces during daily use. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing a zeolite-modified polypropylene material. The zeolite-modified polypropylene material prepared by the method of the present invention has high tensile strength and impact strength, and can have a good application effect in the field of plastic flower pots.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions: A method for preparing a zeolite-modified polypropylene material comprises the following steps: (1) calcining the zeolite powder to obtain pretreated zeolite powder; (2) adding pretreated zeolite powder to an aqueous solution of sodium dodecylbenzene sulfonate, heating the solution to 60-70°C for constant temperature stirring, then cooling the solution to room temperature, filtering, washing, and drying the solution to obtain sodium dodecylbenzene sulfonate modified zeolite; then stirring and mixing the sodium dodecylbenzene sulfonate modified zeolite with citric acid and deionized water to obtain a mixed solution; placing the mixed solution in a reaction kettle, sealing the reaction kettle, heating the solution to 90-95°C for constant temperature stirring, then cooling the solution to room temperature, filtering, washing, and drying the solution to obtain a carboxylated zeolite; (3) adding carboxylated zeolite and amino cage-type polysilsesquioxane to an organic solvent, stirring and mixing, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stirring and mixing, heating to 55-70° C. and stirring at a constant temperature; then cooling to room temperature, filtering, washing, and drying to obtain cage-type polysilsesquioxane modified zeolite; (4) Polypropylene, maleic anhydride grafted polypropylene, cage-type polysilsesquioxane modified zeolite, and antioxidant are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite-modified polypropylene material.

[0007] Preferably, the step (1) specifically comprises the following steps: placing the zeolite powder in a calcining furnace, heating the temperature to 520-580°C at a rate of 10-18°C / min, and calcining for 40-60 min, and then cooling the furnace to room temperature to obtain pretreated zeolite powder.

[0008] Preferably, in step (1), the particle size of the zeolite powder is 150-200 mesh.

[0009] Preferably, in step (2), the mass fraction of the sodium dodecylbenzene sulfonate aqueous solution is 4-9%, and the mass ratio of the pretreated zeolite powder to the sodium dodecylbenzene sulfonate aqueous solution is 1:12-18; The mass ratio of the sodium dodecylbenzene sulfonate modified zeolite, citric acid and deionized water is 1:0.2-0.3:4.5-6.

[0010] Preferably, in step (2), the temperature is raised to 60-70°C and stirred at a constant temperature for 10-15 hours; the temperature is raised to 90-95°C and stirred at a constant temperature for 4.5-7 hours; In step (3), the temperature is raised to 55-70° C. and the stirring is performed at a constant temperature for 2-3 hours.

[0011] Preferably, in step (3), the mass ratio of the carboxylated zeolite, amino cage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, and tetrahydrofuran is 1:0.3-0.6:0.05-0.09:0.04-0.06:11-15.

[0012] Preferably, in step (3), the organic solvent is tetrahydrofuran or chloroform.

[0013] Preferably, in step (4), the zeolite-modified polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene, 6-12 parts of maleic anhydride grafted polypropylene, 18-25 parts of cage-type polysilsesquioxane-modified zeolite, and 0.2-0.5 parts of antioxidant. By combining an appropriate amount of maleic anhydride grafted polypropylene, the bonding strength between the cage-type polysilsesquioxane-modified zeolite and the polypropylene can be enhanced.

[0014] Preferably, the antioxidant is one or a combination of antioxidant 1010 and antioxidant 1076.

[0015] Preferably, the temperature of each zone of the twin-screw extruder is: zone 1: 170-175°C; zone 2: 180-185°C; zone 3: 190-195°C; zone 4: 200-205°C; zone 5: 205-210°C; zone 6: 215-220°C; zone 7: 215-220°C; head: 215-220°C.

[0016] The beneficial effects of the present invention are: The present invention first adopts sodium dodecylbenzene sulfonate modification to the pre-treated zeolite powder after calcination, because sodium dodecylbenzene sulfonate has hydrophilic group and hydrophobic group, it is inserted between zeolite powder structure, by long-time stirring and mixing, zeolite powder is kept higher dispersibility, then citric acid is adopted and combined with hydrothermal reaction to carboxylate zeolite powder, by citric acid modification, the zeolite powder obtained is not only excellent in dispersibility, and the carboxyl group on the surface is abundant. Afterwards, modified zeolite is placed in an organic solvent, and amino cage type polysilsesquioxane is added, by the catalysis of N-hydroxysuccinimide and the activation of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, amino cage type polysilsesquioxane is reacted with carboxyl, and then amino cage type polysilsesquioxane is grafted on the zeolite surface. The zeolite powder modified by the above method not only has excellent dispersibility, but also the organic groups on the surface of the zeolite powder interact with the polypropylene molecular chains, the compatibility between the zeolite powder and polypropylene is significantly enhanced, and the tensile strength and impact strength of the obtained polypropylene composite material are significantly enhanced.

[0017] In addition, the present invention firstly calcines the zeolite to further increase the porosity and dispersibility of the zeolite powder, so that it can be better dispersed and fixed in the polypropylene, and the ion exchange performance of the zeolite powder is improved by calcination, thereby making the subsequent modification effect stronger.

[0018] The zeolite-modified polypropylene material prepared by the method of the present invention is used to prepare a plastic flower pot, which can not only improve the air permeability of the plastic flower pot, but also prevent the plastic flower pot from being damaged when it is collided or dropped. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] The polypropylene used in the present invention is produced by Sinopec Yanshan, with a model of K8003, and the maleic anhydride grafted polypropylene is produced by Arkema of France, with a brand of 18732.

[0021] Embodiment 1: A method for preparing a zeolite-modified polypropylene material comprises the following steps: (1) Place zeolite powder with a particle size of 150-200 mesh in a calcining furnace, heat it to 550°C at a rate of 15°C / min, keep it at that temperature for 60 minutes, and then cool it to room temperature in the furnace to obtain pretreated zeolite powder.

[0022] (2) Pretreated zeolite powder was added to a 9% sodium dodecylbenzene sulfonate aqueous solution in a mass ratio of 1:15. The mixture was heated to 70°C and stirred at a constant temperature for 12 hours, then cooled to room temperature, filtered, washed, and dried to obtain sodium dodecylbenzene sulfonate modified zeolite. The sodium dodecylbenzene sulfonate modified zeolite was then stirred with citric acid and deionized water in a mass ratio of 1:0.2:5 to obtain a mixed solution. The mixed solution was placed in a reactor, and the reactor was sealed. The mixture was then heated to 95°C and stirred at a constant temperature for 6 hours. The mixture was then cooled to room temperature, filtered, washed, and dried to obtain a carboxylated zeolite.

[0023] (3) Add carboxylated zeolite and amino cage-type polysilsesquioxane to tetrahydrofuran, stir and mix, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stir and mix, heat to 60°C and stir at constant temperature for 3 hours, the mass ratio of carboxylated zeolite, amino cage-type polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.4:0.06:0.05:13; then cool to room temperature, filter, wash and dry to obtain cage-type polysilsesquioxane modified zeolite.

[0024] (4) 100 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 25 parts of cage-type polysilsesquioxane modified zeolite, and 0.3 parts of antioxidant 1010 are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite modified polypropylene material. The temperatures of the zones of the twin-screw extruder are: zone 1: 170°C; zone 2: 180°C; zone 3: 195°C; zone 4: 200°C; zone 5: 205°C; zone 6: 215°C; zone 7: 220°C; die head: 220°C.

[0025] Embodiment 2: A method for preparing a zeolite-modified polypropylene material comprises the following steps: (1) Place zeolite powder with a particle size of 150-200 mesh in a calcining furnace, heat it to 530°C at a rate of 18°C / min, keep it warm and calcine it for 50 minutes, and then cool it to room temperature in the furnace to obtain pretreated zeolite powder.

[0026] (2) Pretreated zeolite powder was added to a 7% sodium dodecylbenzene sulfonate aqueous solution, the mass ratio of the pretreated zeolite powder to the sodium dodecylbenzene sulfonate aqueous solution being 1:18, the temperature was raised to 60°C and stirred at a constant temperature for 12 hours, then cooled to room temperature, filtered, washed, and dried to obtain sodium dodecylbenzene sulfonate modified zeolite; the sodium dodecylbenzene sulfonate modified zeolite was then stirred and mixed with citric acid and deionized water in a mass ratio of 1:0.3:6 to obtain a mixed solution; the mixed solution was placed in a reactor, the reactor was sealed, the temperature was raised to 90°C and stirred at a constant temperature for 7 hours, then cooled to room temperature, filtered, washed, and dried to obtain a carboxylated zeolite.

[0027] (3) Add carboxylated zeolite and amino cage-type polysilsesquioxane to tetrahydrofuran, stir and mix, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stir and mix, heat to 55°C and stir at constant temperature for 3 hours, the mass ratio of carboxylated zeolite, amino cage-type polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.5:0.08:0.06:15; then cool to room temperature, filter, wash and dry to obtain cage-type polysilsesquioxane modified zeolite.

[0028] (4) 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 22 parts of cage-type polysilsesquioxane modified zeolite, and 0.2 parts of antioxidant 1010 are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite modified polypropylene material. The temperatures of the zones of the twin-screw extruder are: zone 1: 170°C; zone 2: 180°C; zone 3: 195°C; zone 4: 200°C; zone 5: 205°C; zone 6: 215°C; zone 7: 220°C; die head: 220°C.

[0029] Embodiment 3: A method for preparing a zeolite-modified polypropylene material comprises the following steps: (1) Place zeolite powder with a particle size of 150-200 mesh in a calcining furnace, heat it to 520°C at a rate of 18°C / min, keep it warm and calcine it for 60 minutes, and then cool it to room temperature in the furnace to obtain pretreated zeolite powder.

[0030] (2) Pretreated zeolite powder was added to a 5% sodium dodecylbenzene sulfonate aqueous solution, the mass ratio of the pretreated zeolite powder to the sodium dodecylbenzene sulfonate aqueous solution being 1:12, the temperature was raised to 65°C and stirred at a constant temperature for 10 hours, then cooled to room temperature, filtered, washed, and dried to obtain sodium dodecylbenzene sulfonate modified zeolite; the sodium dodecylbenzene sulfonate modified zeolite was then stirred and mixed with citric acid and deionized water in a mass ratio of 1:0.2:4.5 to obtain a mixed solution; the mixed solution was placed in a reactor, and the reactor was sealed, and the temperature was raised to 92°C and stirred at a constant temperature for 4.5 hours, then cooled to room temperature, filtered, washed, and dried to obtain a carboxylated zeolite.

[0031] (3) Add carboxylated zeolite and amino cage-type polysilsesquioxane to tetrahydrofuran, stir and mix, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stir and mix, heat to 70°C and stir at constant temperature for 3 hours, the mass ratio of carboxylated zeolite, amino cage-type polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.3:0.08:0.04:11; then cool to room temperature, filter, wash and dry to obtain cage-type polysilsesquioxane modified zeolite.

[0032] (4) 100 parts of polypropylene, 6 parts of maleic anhydride grafted polypropylene, 18 parts of cage-type polysilsesquioxane modified zeolite, and 0.2 parts of antioxidant 1010 are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite modified polypropylene material. The temperatures of the zones of the twin-screw extruder are: zone 1: 170°C; zone 2: 185°C; zone 3: 190°C; zone 4: 205°C; zone 5: 210°C; zone 6: 220°C; zone 7: 220°C; die head: 220°C.

[0033] Embodiment 4: A method for preparing a zeolite-modified polypropylene material comprises the following steps: (1) Place zeolite powder with a particle size of 150-200 mesh in a calcining furnace, heat it to 550°C at a rate of 10°C / min, keep it at that temperature and calcine it for 60 minutes, and then cool it to room temperature in the furnace to obtain pretreated zeolite powder.

[0034] (2) Pretreated zeolite powder was added to a 4% sodium dodecylbenzene sulfonate aqueous solution, the mass ratio of the pretreated zeolite powder to the sodium dodecylbenzene sulfonate aqueous solution being 1:16, the temperature was raised to 67°C and stirred at a constant temperature for 15 hours, then cooled to room temperature, filtered, washed, and dried to obtain sodium dodecylbenzene sulfonate modified zeolite; the sodium dodecylbenzene sulfonate modified zeolite was then stirred and mixed with citric acid and deionized water in a mass ratio of 1:0.3:6 to obtain a mixed solution; the mixed solution was placed in a reactor, and the reactor was sealed, and the temperature was raised to 95°C and stirred at a constant temperature for 4.5 hours, then cooled to room temperature, filtered, washed, and dried to obtain a carboxylated zeolite.

[0035] (3) Add carboxylated zeolite and amino cage-type polysilsesquioxane to tetrahydrofuran, stir and mix, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stir and mix, heat to 60°C and stir at constant temperature for 2 hours, the mass ratio of carboxylated zeolite, amino cage-type polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.5:0.05:0.06:12; then cool to room temperature, filter, wash and dry to obtain cage-type polysilsesquioxane modified zeolite.

[0036] (4) 100 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 20 parts of cage-type polysilsesquioxane modified zeolite, and 0.5 parts of antioxidant 1010 are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite modified polypropylene material. The temperatures of the zones of the twin-screw extruder are: zone 1: 175°C; zone 2: 180°C; zone 3: 190°C; zone 4: 205°C; zone 5: 205°C; zone 6: 215°C; zone 7: 215°C; die head: 215°C.

[0037] Embodiment 5: A method for preparing a zeolite-modified polypropylene material comprises the following steps: (1) Place zeolite powder with a particle size of 150-200 mesh in a calcining furnace, heat it to 580°C at a rate of 13°C / min, keep it warm and calcine it for 40 minutes, and then cool it to room temperature in the furnace to obtain pretreated zeolite powder.

[0038] (2) Pretreated zeolite powder was added to a 7% sodium dodecylbenzene sulfonate aqueous solution, the mass ratio of the pretreated zeolite powder to the sodium dodecylbenzene sulfonate aqueous solution being 1:15, the temperature was raised to 60°C and stirred at a constant temperature for 10 hours, then cooled to room temperature, filtered, washed, and dried to obtain sodium dodecylbenzene sulfonate modified zeolite; the sodium dodecylbenzene sulfonate modified zeolite was then stirred and mixed with citric acid and deionized water in a mass ratio of 1:0.2:5.5 to obtain a mixed solution; the mixed solution was placed in a reactor, the reactor was sealed, the temperature was raised to 90°C and stirred at a constant temperature for 6 hours, then cooled to room temperature, filtered, washed, and dried to obtain a carboxylated zeolite.

[0039] (3) Add carboxylated zeolite and amino cage-type polysilsesquioxane to tetrahydrofuran, stir and mix, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stir and mix, heat to 55°C and stir at constant temperature for 3 hours, the mass ratio of carboxylated zeolite, amino cage-type polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.6:0.09:0.05:15; then cool to room temperature, filter, wash and dry to obtain cage-type polysilsesquioxane modified zeolite.

[0040] (4) 100 parts of polypropylene, 12 parts of maleic anhydride grafted polypropylene, 22 parts of cage-type polysilsesquioxane modified zeolite, and 0.3 parts of antioxidant 1010 are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite modified polypropylene material. The temperature of each zone of the twin-screw extruder is: zone 1: 175°C; zone 2: 185°C; zone 3: -195°C; zone 4: 200°C; zone 5: 210°C; zone 6: 215°C; zone 7: 220°C; die head: 220°C.

[0041] Embodiment 6: A method for preparing a zeolite-modified polypropylene material comprises the following steps: (1) Place zeolite powder with a particle size of 150-200 mesh in a calcining furnace, heat it to 550°C at a rate of 15°C / min, keep it at that temperature for 50 minutes, and then cool it to room temperature in the furnace to obtain pretreated zeolite powder.

[0042] (2) Pretreated zeolite powder was added to a 5% sodium dodecylbenzene sulfonate aqueous solution, the mass ratio of the pretreated zeolite powder to the sodium dodecylbenzene sulfonate aqueous solution being 1:12, the temperature was raised to 60°C and stirred at a constant temperature for 12 hours, then cooled to room temperature, filtered, washed, and dried to obtain sodium dodecylbenzene sulfonate modified zeolite; the sodium dodecylbenzene sulfonate modified zeolite was then stirred and mixed with citric acid and deionized water in a mass ratio of 1:0.2:6 to obtain a mixed solution; the mixed solution was placed in a reactor, the reactor was sealed, the temperature was raised to 90°C and stirred at a constant temperature for 5 hours, then cooled to room temperature, filtered, washed, and dried to obtain a carboxylated zeolite.

[0043] (3) Add carboxylated zeolite and amino cage-type polysilsesquioxane to tetrahydrofuran, stir and mix, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stir and mix, heat to 70°C and stir at constant temperature for 2 hours, the mass ratio of carboxylated zeolite, amino cage-type polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.3:0.05:0.06:13; then cool to room temperature, filter, wash and dry to obtain cage-type polysilsesquioxane modified zeolite.

[0044] (4) 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 23 parts of cage-type polysilsesquioxane modified zeolite, and 0.3 parts of antioxidant 1010 are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite-modified polypropylene material. The temperatures of the zones of the twin-screw extruder are: zone 1: 175°C; zone 2: 185°C; zone 3: 195°C; zone 4: 205°C; zone 5: 205°C; zone 6: 215°C; zone 7: 215°C; die head: 215°C.

[0045] Comparative Example 1: Unlike Example 6, step (2) of the preparation method of zeolite-modified polypropylene material in this comparative example includes the following steps: stirring and mixing the pretreated zeolite with citric acid and deionized water in a mass ratio of 1:0.2:6 to obtain a mixed solution; placing the mixed solution in a reaction kettle, sealing the reaction kettle, heating it to 90°C and stirring at a constant temperature for 5 hours, cooling it to room temperature, filtering, washing, and drying to obtain a carboxylated zeolite.

[0046] The remaining steps (1), (3), and (4) are basically the same as those in Example 6.

[0047] Comparative Example 2: Unlike Example 6, step (2) of the preparation method of the zeolite-modified polypropylene material in this comparative example includes the following steps: adding pretreated zeolite powder to a 5% sodium dodecylbenzene sulfonate aqueous solution, the mass ratio of the pretreated zeolite powder to the sodium dodecylbenzene sulfonate aqueous solution being 1:12, heating the mixture to 60°C and stirring at a constant temperature for 12 hours, then cooling the mixture to room temperature, filtering, washing, and drying to obtain sodium dodecylbenzene sulfonate modified zeolite; then stirring and mixing the sodium dodecylbenzene sulfonate modified zeolite with citric acid and deionized water in a mass ratio of 1:0.2:6 to obtain a mixed solution; heating the mixed solution to 60°C and stirring at a constant temperature for 10 hours (without performing a hydrothermal reaction), then cooling the mixture to room temperature, filtering, washing, and drying to obtain a carboxylated zeolite.

[0048] The remaining steps (1), (3), and (4) are basically the same as those in Example 6.

[0049] Comparative Example 3: The preparation method of the zeolite-modified polypropylene material of this comparative example comprises the following steps: (1) Add zeolite powder with a particle size of 150-200 mesh and amino cage polysilsesquioxane to tetrahydrofuran, stir and mix, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stir and mix, heat to 70°C and stir at constant temperature for 2 hours, the mass ratio of zeolite powder, amino cage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.3:0.05:0.06:13; then cool to room temperature, filter, wash and dry to obtain cage polysilsesquioxane modified zeolite.

[0050] (2) 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 23 parts of cage-type polysilsesquioxane modified zeolite, and 0.3 parts of antioxidant 1010 are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite modified polypropylene material. The temperatures of the zones of the twin-screw extruder are: zone 1: 175°C; zone 2: 185°C; zone 3: 195°C; zone 4: 205°C; zone 5: 205°C; zone 6: 215°C; zone 7: 215°C; die head: 215°C.

[0051] Comparative Example 4: The preparation method of the zeolite-modified polypropylene material of this comparative example comprises the following steps: (1) Place zeolite powder with a particle size of 150-200 mesh in a calcining furnace, heat it to 550°C at a rate of 15°C / min, keep it at that temperature for 50 min, and then cool it to room temperature in the furnace to obtain pretreated zeolite powder.

[0052] (2) adding pretreated zeolite powder to a 5% sodium dodecylbenzene sulfonate aqueous solution, wherein the mass ratio of the pretreated zeolite powder to the sodium dodecylbenzene sulfonate aqueous solution is 1:12, heating the mixture to 60°C and stirring the mixture at a constant temperature for 12 hours, then cooling the mixture to room temperature, filtering, washing and drying the mixture to obtain a sodium dodecylbenzene sulfonate modified zeolite; (3) 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 23 parts of sodium dodecylbenzene sulfonate modified zeolite, and 0.3 parts of antioxidant 1010 are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite modified polypropylene material. The temperatures of the zones of the twin-screw extruder are: zone 1: 175°C; zone 2: 185°C; zone 3: 195°C; zone 4: 205°C; zone 5: 205°C; zone 6: 215°C; zone 7: 215°C; die head: 215°C.

[0053] Comparative Example 5: The preparation method of the zeolite-modified polypropylene material of this comparative example comprises the following steps: 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 23 parts of zeolite powder (particle size of 150-200 meshes), and 0.3 parts of antioxidant 1010 are mixed to obtain a mixture, and then the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite modified polypropylene material. The temperature of each zone of the twin-screw extruder is: zone 1: 175°C; zone 2: 185°C; zone 3: 195°C; zone 4: 205°C; zone 5: 205°C; zone 6: 215°C; zone 7: 215°C; head: 215°C.

[0054] Performance Testing: The zeolite-modified polypropylene materials in Examples 1-6 and Comparative Examples 1-5 were injection molded into tensile bars (length 150 mm × width 10 mm × thickness 4 mm) and impact bars (length 80 mm × width 10 mm × thickness 4 mm, with a notch residual width of 8 mm) in an injection molding machine. The tensile strength test was performed according to the method in GB / T1040.1-2018 "Determination of tensile properties of plastics", and the notched impact strength test was performed according to the method in GB / T1843-2008 "Determination of cantilever beam impact strength of plastics".

[0055] Table 1 Test results of tensile strength and elongation at break

[0056] It can be seen from Table 1 that the zeolite-modified polypropylene materials prepared by the cage-type polysilsesquioxane-modified zeolite in the embodiments of the present invention have high tensile strength and impact strength. From the comparison between Example 6 and Comparative Example 5, it can be seen that the strength and impact resistance of the polypropylene material can be significantly improved by modifying the zeolite using the method of the present invention.

[0057] From the comparison between Example 6 and Comparative Example 1, it can be seen that if the zeolite is not modified with sodium dodecylbenzene sulfonate, the strength and impact resistance of the zeolite-modified polypropylene material will be reduced. From the comparison between Example 6 and Comparative Example 2, it can be seen that in the process of preparing the carboxylated zeolite, if the hydrothermal reaction is not performed, the strength and impact resistance of the obtained zeolite-modified polypropylene material will be reduced.

[0058] From the comparison between Example 6 and Comparative Example 3, it can be seen that if the zeolite is not modified with sodium dodecylbenzene sulfonate and carboxylated, or if the zeolite is directly modified with sodium dodecylbenzene sulfonate to prepare the zeolite-modified polypropylene material, the strength and impact resistance of the zeolite-modified polypropylene material will be significantly reduced.

[0059] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a zeolite-modified polypropylene material, characterized in that: The following steps are involved: (1) calcining the zeolite powder to obtain pretreated zeolite powder; (2) adding pretreated zeolite powder to an aqueous solution of sodium dodecylbenzene sulfonate, heating the solution to 60-70°C for constant temperature stirring, then cooling the solution to room temperature, filtering, washing, and drying the solution to obtain sodium dodecylbenzene sulfonate modified zeolite; then stirring and mixing the sodium dodecylbenzene sulfonate modified zeolite with citric acid and deionized water to obtain a mixed solution; placing the mixed solution in a reaction kettle, sealing the reaction kettle, heating the solution to 90-95°C for constant temperature stirring, then cooling the solution to room temperature, filtering, washing, and drying the solution to obtain a carboxylated zeolite; (3) adding carboxylated zeolite and amino cage-type polysilsesquioxane to an organic solvent, stirring and mixing, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stirring and mixing, heating to 55-70° C. and stirring at a constant temperature; then cooling to room temperature, filtering, washing, and drying to obtain cage-type polysilsesquioxane modified zeolite; (4) Polypropylene, maleic anhydride grafted polypropylene, cage-type polysilsesquioxane modified zeolite, and antioxidant are mixed to obtain a mixture, and the mixture is placed in a twin-screw extruder for melt blending, extrusion, and granulation to obtain the zeolite-modified polypropylene material.

2. The method for preparing the zeolite-modified polypropylene material according to claim 1, characterized in that: The step (1) specifically comprises the following steps: placing the zeolite powder in a calcining furnace, heating the temperature to 520-580°C at a rate of 10-18°C / min, maintaining the temperature and calcining for 40-60min, and then cooling the furnace to room temperature to obtain pretreated zeolite powder.

3. The method for preparing the zeolite-modified polypropylene material according to claim 1, characterized in that: In step (1), the particle size of the zeolite powder is 150-200 mesh.

4. The method for preparing the zeolite-modified polypropylene material according to claim 1, characterized in that: In step (2), the mass fraction of the sodium dodecylbenzene sulfonate aqueous solution is 4-9%, and the mass ratio of the pretreated zeolite powder to the sodium dodecylbenzene sulfonate aqueous solution is 1:12-18; The mass ratio of the sodium dodecylbenzene sulfonate modified zeolite, citric acid and deionized water is 1:0.2-0.3:4.5-6.

5. The method for preparing the zeolite-modified polypropylene material according to claim 1, characterized in that: In step (2), the temperature is raised to 60-70°C and stirred at a constant temperature for 10-15 hours; the temperature is raised to 90-95°C and stirred at a constant temperature for 4.5-7 hours; In step (3), the temperature is raised to 55-70° C. and the stirring is performed at a constant temperature for 2-3 hours.

6. The method for preparing the zeolite-modified polypropylene material according to claim 1, characterized in that: In step (3), the mass ratio of the carboxylated zeolite, amino cage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, and tetrahydrofuran is 1:0.3-0.6:0.05-0.09:0.04-0.06:11-15.

7. The method for preparing the zeolite-modified polypropylene material according to claim 1, characterized in that: In step (3), the organic solvent is tetrahydrofuran or chloroform.

8. The method for preparing the zeolite-modified polypropylene material according to claim 1, characterized in that: In step (4), the zeolite-modified polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene, 6-12 parts of maleic anhydride-grafted polypropylene, 18-25 parts of cage-type polysilsesquioxane-modified zeolite, and 0.2-0.5 parts of antioxidant.

9. The method for preparing the zeolite-modified polypropylene material according to claim 8, characterized in that: The antioxidant is one of the antioxidant 1010 and the antioxidant 1076 or a combination of both.

10. The method for preparing the zeolite-modified polypropylene material according to claim 1, characterized in that: The temperature of each zone of the twin-screw extruder is: zone 1: 170-175°C; zone 2: 180-185°C; zone 3: 190-195°C; zone 4: 200-205°C; zone 5: 205-210°C; zone 6: 215-220°C; zone 7: 215-220°C; Machine head: 215-220℃.

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