A method for preparing a zeolite-modified polypropylene material

Abstract

The application provides a preparation method of a zeolite modified polypropylene material, and comprises the following steps: (1) performing calcination treatment on 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 cage polysilsesquioxane modified zeolite by using an organic solvent, the carboxylated zeolite, amino cage polysilsesquioxane and -(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide; (4) mixing polypropylene, maleic anhydride grafted polypropylene, cage polysilsesquioxane modified zeolite and an antioxidant to obtain a mixture, and then placing the mixture in a double-screw extruder to perform melt blending, extrusion and granulation. The zeolite modified polypropylene material prepared by the method has high tensile strength and impact strength, and can have good application effect in the field of plastic flowerpots.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a preparation method of zeolite modified polypropylene material. BACKGROUND

[0002] As a vessel for planting flowers, flowerpots are indispensable in gardening and home decoration. The materials of flowerpots are various, including ceramic flowerpots, plastic flowerpots, metal flowerpots, glass flowerpots, etc. Among them, plastic flowerpots have the advantages of certain toughness, not easy to break, can withstand the collision and falling in daily use, light weight and affordable price, etc., so the application of plastic in the field of gardening is becoming more and more widely. Polypropylene is often used to prepare plastic flowerpots because of its good toughness, rigidity and corrosion resistance.

[0003] However, a good performance flowerpot not only needs to provide sufficient growing space for the flowers and plants, but also needs to have good air permeability. But the flowerpots directly prepared by polypropylene have poor air permeability, 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 for filling modification. Zeolite is a silicate with a skeleton of silicon-oxygen tetrahedron and aluminum-oxygen tetrahedron. Its skeleton structure contains a large number of uniform cavities and channels inside, and the electronegativity generated by silicon-oxygen and aluminum-oxygen structure and the large specific surface area generated by a large number of microporous structure endow zeolite with high ion adsorption capacity and ion exchange capacity. However, because zeolite is a hydrophilic material and polypropylene is a lipophilic material, their compatibility is poor. If a large amount of zeolite is compounded with polypropylene, although the air permeability of the polypropylene material is enhanced, the impact resistance of the obtained polypropylene composite material is reduced, so that the polypropylene plastic flowerpot is easily damaged by external force in daily use. SUMMARY

[0005] The purpose of the present application is to provide a preparation method of zeolite modified polypropylene material. The zeolite modified polypropylene material prepared by the method has high tensile strength and impact strength, and can have good application effect in the field of plastic flowerpots.

[0006] To achieve the above purpose, the present application is realized by the following technical scheme:

[0007] A preparation method of zeolite modified polypropylene material, comprising the following steps:

[0008] (1) The zeolite powder is calcined to obtain pretreated zeolite powder;

[0009] (2) adding the pretreated zeolite powder into the aqueous solution of sodium dodecyl benzene sulfonate, heating to 60-70℃ and constant temperature stirring, then cooling to room temperature, filtering, washing and drying to obtain the sodium dodecyl benzene sulfonate modified zeolite; then mixing the sodium dodecyl benzene sulfonate modified zeolite with citric acid and deionized water to obtain a mixed solution; placing the mixed solution in a reaction kettle and sealing the reaction kettle, then heating to 90-95℃ and constant temperature stirring, cooling to room temperature, filtering, washing and drying to obtain the carboxylated zeolite;

[0010] (3) adding the carboxylated zeolite and the aminocage polysilsesquioxane into the organic solvent, mixing, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, mixing, heating to 55-70℃ and constant temperature stirring, then cooling to room temperature, filtering, washing and drying to obtain the cage polysilsesquioxane modified zeolite;

[0011] (4) mixing the polypropylene, the maleic anhydride grafted polypropylene, the cage polysilsesquioxane modified zeolite and the antioxidant to obtain a mixed material, then placing the mixed material in a twin-screw extruder for melt blending, extruding and granulating to obtain the zeolite modified polypropylene material.

[0012] Preferably, the step (1) specifically comprises the following steps: placing the zeolite powder in a calcination furnace, heating to 520-580℃ at a rate of 10-18℃ / min, keeping the temperature for 40-60min, then cooling to room temperature with the furnace to obtain the pretreated zeolite powder.

[0013] Preferably, in the step (1), the particle size of the zeolite powder is 150-200 mesh.

[0014] Preferably, in the step (2), the mass fraction of the aqueous solution of sodium dodecyl benzene sulfonate is 4-9%, and the mass ratio of the pretreated zeolite powder to the aqueous solution of sodium dodecyl benzene sulfonate is 1:12-18.

[0015] The mass ratio of the sodium dodecyl benzene sulfonate modified zeolite, the citric acid and the deionized water is 1:0.2-0.3:4.5-6.

[0016] Preferably, in the step (2), the time for heating to 60-70℃ and constant temperature stirring is 10-15h, and the time for heating to 90-95℃ and constant temperature stirring is 4.5-7h.

[0017] In the step (3), the time for heating to 55-70℃ and constant temperature stirring is 2-3h.

[0018] Preferably, in step (3), the mass ratio of the carboxylated zeolite, the amino cage polysilsesquioxane, the 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, the N-hydroxysuccinimide, the tetrahydrofuran and the chloroform is 1:0.3-0.6:0.05-0.09:0.04-0.06:11-15:0.3-0.6.

[0019] Preferably, in step (3), the organic solvent is tetrahydrofuran or chloroform.

[0020] Preferably, in step (4), the zeolite modified polypropylene material comprises the following raw materials by weight: polypropylene 100 parts, maleic anhydride grafted polypropylene 6-12 parts, cage polysilsesquioxane modified zeolite 18-25 parts, and antioxidant 0.2-0.5 parts. By combining an appropriate amount of maleic anhydride grafted polypropylene, the bonding force between the cage polysilsesquioxane modified zeolite and the polypropylene can be improved.

[0021] Preferably, the antioxidant is one or a combination of antioxidants 1010 and 1076.

[0022] Preferably, the temperature of each zone of the twin-screw extruder is as follows: zone 1: 170-175℃; zone 2: 180-185℃; zone 3: 190-195℃; zone 4: 200-205℃; zone 5: 205-210℃; zone 6: 215-220℃; zone 7: 215-220℃; and the die head: 215-220℃.

[0023] The beneficial effects of the present application are as follows:

[0024] The calcined pretreated zeolite powder is first modified by sodium dodecyl benzene sulfonate. Since sodium dodecyl benzene sulfonate has hydrophilic groups and hydrophobic groups, it is inserted between the structure of the zeolite powder. By long-time stirring and mixing, the zeolite powder maintains high dispersibility. Then, the zeolite powder is carboxylated by citric acid and combined with hydrothermal reaction. Through citric acid modification, the obtained zeolite powder not only has excellent dispersibility, but also has a rich carboxyl group on the surface. Then, the modified zeolite is placed in an organic solvent and amino cage polysilsesquioxane is added. Through the catalytic action of N-hydroxysuccinimide and the activation of 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, the amino cage polysilsesquioxane reacts with the carboxyl group, and then the amino cage polysilsesquioxane is grafted onto the surface of the zeolite. The zeolite powder modified by the above method not only has excellent dispersibility, but also has interaction between the organic groups on the surface of the zeolite powder and the polypropylene molecular chain. The compatibility between the zeolite powder and the polypropylene is significantly enhanced, and the tensile strength and impact strength of the obtained polypropylene composite material are significantly improved.

[0025] In addition, the zeolite is first calcined, so that the porosity and dispersibility of the zeolite powder are further increased, the zeolite powder is better dispersed and fixed in the polypropylene, and the ion exchange performance of the zeolite powder is better through calcination, so that the subsequent modification effect is stronger.

[0026] The zeolite modified polypropylene material prepared by the method has good dispersibility and is not easy to be damaged when the plastic flowerpot is collided or dropped. DETAILED DESCRIPTION

[0027] To make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0028] The polypropylene used in the present application is K8003 from Sinopec Yanshan, and the maleic anhydride grafted polypropylene is 18732 from Arkema, France.

[0029] Embodiment 1

[0030] A preparation method of a zeolite modified polypropylene material, comprising the following steps:

[0031] (1) The zeolite powder with a particle size of 150-200 mesh is placed in a calcination furnace, and heated at a rate of 15℃ / min to 550℃ and calcined for 60 min, and then cooled to room temperature with the furnace, to obtain pretreated zeolite powder.

[0032] (2) The pretreated zeolite powder is added to a 9% sodium dodecyl benzene sulfonate aqueous solution, and the mass ratio of the pretreated zeolite powder to the sodium dodecyl benzene sulfonate aqueous solution is 1:15, and then heated to 70℃ for constant temperature stirring for 12 h, and then cooled to room temperature, and then filtered, washed and dried to obtain sodium dodecyl benzene sulfonate modified zeolite; then the sodium dodecyl benzene sulfonate modified zeolite is mixed with citric acid and deionized water at a mass ratio of 1:0.2:5 to obtain a mixed solution; the mixed solution is placed in a reaction kettle and the reaction kettle is closed, then heated to 95℃ for constant temperature stirring for 6 h, and then cooled to room temperature, and then filtered, washed and dried to obtain carboxylated zeolite.

[0033] (3) adding carboxylated zeolite and aminocage polysilsesquioxane into tetrahydrofuran, stirring and mixing, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stirring and mixing, then heating to 60℃ and constant temperature stirring for 3h, the mass ratio of carboxylated zeolite, aminocage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.4:0.06:0.05:13; then cooling to room temperature, filtering, washing and drying to obtain cage polysilsesquioxane modified zeolite.

[0034] (4) mixing 100 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 25 parts of cage polysilsesquioxane modified zeolite and 0.3 parts of antioxidant 1010 to obtain a mixture, then melting blending, extruding and granulating the mixture in a twin-screw extruder to obtain the zeolite modified polypropylene material. The temperature of each zone of the twin-screw extruder is as follows: zone 1: 170℃; zone 2: 180℃; zone 3: 195℃; zone 4: 200℃; zone 5: 205℃; zone 6: 215℃; zone 7: 220℃; die head: 220℃.

[0035] Example 2:

[0036] A method for preparing a zeolite modified polypropylene material, comprising the following steps:

[0037] (1) placing zeolite powder with a particle size of 150-200 mesh into a calcination furnace, heating to 530℃ at a rate of 18℃ / min, and keeping the temperature for calcination for 50min, then cooling to room temperature with the furnace to obtain pretreated zeolite powder.

[0038] (2) adding pretreated zeolite powder into a 7% sodium dodecyl benzene sulfonate aqueous solution, the mass ratio of pretreated zeolite powder to sodium dodecyl benzene sulfonate aqueous solution is 1:18, heating to 60℃ and constant temperature stirring for 12h, then cooling to room temperature, filtering, washing and drying to obtain sodium dodecyl benzene sulfonate modified zeolite; then stirring and mixing sodium dodecyl benzene sulfonate modified zeolite, citric acid and deionized water according to a mass ratio of 1:0.3:6 to obtain a mixed solution; placing the mixed solution in a reaction kettle and sealing the reaction kettle, then heating to 90℃ and constant temperature stirring for 7h, then cooling to room temperature, filtering, washing and drying to obtain carboxylated zeolite.

[0039] (3) adding carboxylated zeolite and aminocage polysilsesquioxane into tetrahydrofuran, stirring and mixing, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stirring and mixing, then heating to 55℃ and constant temperature stirring for 3h, the mass ratio of carboxylated zeolite, aminocage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.5:0.08:0.06:15; then cooling to room temperature, filtering, washing and drying to obtain cage polysilsesquioxane modified zeolite.

[0040] (4) mixing 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 22 parts of cage polysilsesquioxane modified zeolite and 0.2 parts of antioxidant 1010 to obtain a mixture, then melting blending, extruding and granulating the mixture in a twin-screw extruder to obtain the zeolite modified polypropylene material. The temperature of each zone of the twin-screw extruder is as follows: zone 1: 170℃; zone 2: 180℃; zone 3: 195℃; zone 4: 200℃; zone 5: 205℃; zone 6: 215℃; zone 7: 220℃; die head: 220℃.

[0041] Example 3:

[0042] A method for preparing a zeolite modified polypropylene material, comprising the following steps:

[0043] (1) placing zeolite powder with a particle size of 150-200 mesh into a calcination furnace, heating to 520℃ at a rate of 18℃ / min and calcining for 60min, then cooling to room temperature with the furnace to obtain pretreated zeolite powder.

[0044] (2) adding pretreated zeolite powder into a 5% sodium dodecyl benzene sulfonate aqueous solution, the mass ratio of pretreated zeolite powder to sodium dodecyl benzene sulfonate aqueous solution being 1:12, heating to 65℃ and constant temperature stirring for 10h, then cooling to room temperature, filtering, washing and drying to obtain sodium dodecyl benzene sulfonate modified zeolite; then stirring and mixing sodium dodecyl benzene sulfonate modified zeolite, citric acid and deionized water according to a mass ratio of 1:0.2:4.5 to obtain a mixed solution; placing the mixed solution in a reaction kettle and sealing the reaction kettle, then heating to 92℃ and constant temperature stirring for 4.5h, then cooling to room temperature, filtering, washing and drying to obtain carboxylated zeolite.

[0045] (3) adding carboxylated zeolite and aminocage polysilsesquioxane into tetrahydrofuran, stirring and mixing, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stirring and mixing, then heating to 70℃ and constant temperature stirring for 3h, the mass ratio of carboxylated zeolite, aminocage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.3:0.08:0.04:11; then cooling to room temperature, filtering, washing and drying to obtain cage polysilsesquioxane modified zeolite.

[0046] (4) mixing 100 parts of polypropylene, 6 parts of maleic anhydride grafted polypropylene, 18 parts of cage polysilsesquioxane modified zeolite and 0.2 parts of antioxidant 1010 to obtain a mixture, then melting blending, extruding and granulating the mixture in a twin-screw extruder to obtain the zeolite modified polypropylene material. The temperature of each zone of the twin-screw extruder is as follows: zone 1: 170℃; zone 2: 185℃; zone 3: 190℃; zone 4: 205℃; zone 5: 210℃; zone 6: 220℃; zone 7: 220℃; and die head: 220℃.

[0047] Example 4:

[0048] A method for preparing a zeolite modified polypropylene material, comprising the following steps:

[0049] (1) placing zeolite powder with a particle size of 150-200 mesh into a calcination furnace, heating to 550℃ at a rate of 10℃ / min, and calcining for 60min, then cooling to room temperature with the furnace to obtain pretreated zeolite powder.

[0050] (2) adding pretreated zeolite powder into a 4% sodium dodecyl benzene sulfonate aqueous solution, the mass ratio of pretreated zeolite powder to sodium dodecyl benzene sulfonate aqueous solution being 1:16, heating to 67℃ and constant temperature stirring for 15h, then cooling to room temperature, filtering, washing and drying to obtain sodium dodecyl benzene sulfonate modified zeolite; then stirring and mixing the sodium dodecyl benzene sulfonate modified zeolite with citric acid and deionized water according to a mass ratio of 1:0.3:6 to obtain a mixed solution; placing the mixed solution in a reaction kettle and sealing the reaction kettle, then heating to 95℃ and constant temperature stirring for 4.5h, then cooling to room temperature, filtering, washing and drying to obtain carboxylated zeolite.

[0051] (3) adding carboxylated zeolite and aminocage polysilsesquioxane into tetrahydrofuran, stirring and mixing, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stirring and mixing, then heating to 60℃ and constant temperature stirring for 2h, the mass ratio of carboxylated zeolite, aminocage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.5:0.05:0.06:12; then cooling to room temperature, filtering, washing and drying to obtain cage polysilsesquioxane modified zeolite.

[0052] (4) mixing 100 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 20 parts of cage polysilsesquioxane modified zeolite and 0.5 parts of antioxidant 1010 to obtain a mixture, then melting blending, extruding and granulating the mixture in a twin-screw extruder to obtain the zeolite modified polypropylene material. The temperature of each zone of the twin-screw extruder is as follows: zone 1: 175℃; zone 2: 180℃; zone 3: 190℃; zone 4: 205℃; zone 5: 205℃; zone 6: 215℃; zone 7: 215℃; and die head: 215℃.

[0053] Example 5:

[0054] A method for preparing a zeolite modified polypropylene material, comprising the following steps:

[0055] (1) placing zeolite powder with a particle size of 150-200 mesh into a calcination furnace, heating to 580℃ at a rate of 13℃ / min, and calcining for 40min, then cooling to room temperature with the furnace to obtain pretreated zeolite powder.

[0056] (2) adding pretreated zeolite powder into a 7% sodium dodecyl benzene sulfonate aqueous solution, the mass ratio of pretreated zeolite powder to sodium dodecyl benzene sulfonate aqueous solution being 1:15, heating to 60℃ and constant temperature stirring for 10h, then cooling to room temperature, filtering, washing and drying to obtain sodium dodecyl benzene sulfonate modified zeolite; then stirring and mixing the sodium dodecyl benzene sulfonate modified zeolite with citric acid and deionized water according to a mass ratio of 1:0.2:5.5 to obtain a mixed solution; placing the mixed solution in a reaction kettle and sealing the reaction kettle, then heating to 90℃ and constant temperature stirring for 6h, then cooling to room temperature, filtering, washing and drying to obtain carboxylated zeolite.

[0057] (3) adding carboxylated zeolite and aminocage polysilsesquioxane into tetrahydrofuran, stirring and mixing, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stirring and mixing, then heating to 55℃ and constant temperature stirring for 3h, the mass ratio of carboxylated zeolite, aminocage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.6:0.09:0.05:15; then cooling to room temperature, filtering, washing and drying to obtain cage polysilsesquioxane modified zeolite.

[0058] (4) mixing 100 parts of polypropylene, 12 parts of maleic anhydride grafted polypropylene, 22 parts of cage polysilsesquioxane modified zeolite and 0.3 parts of antioxidant 1010 to obtain a mixture, then melting blending, extruding and granulating the mixture in a twin-screw extruder to obtain the zeolite modified polypropylene material. The temperature of each zone of the twin-screw extruder is as follows: zone 1: 175℃; zone 2: 185℃; zone 3: 195℃; zone 4: 200℃; zone 5: 210℃; zone 6: 215℃; zone 7: 220℃; and die head: 220℃.

[0059] Example 6:

[0060] A method for preparing a zeolite modified polypropylene material, comprising the following steps:

[0061] (1) placing zeolite powder with a particle size of 150-200 mesh into a calcination furnace, heating to 550℃ at a rate of 15℃ / min, and calcining for 50min, then cooling to room temperature with the furnace to obtain pretreated zeolite powder.

[0062] (2) adding pretreated zeolite powder into a 5% sodium dodecyl benzene sulfonate aqueous solution, the mass ratio of pretreated zeolite powder to sodium dodecyl benzene sulfonate aqueous solution being 1:12, heating to 60℃ and constant temperature stirring for 12h, then cooling to room temperature, filtering, washing and drying to obtain sodium dodecyl benzene sulfonate modified zeolite; then stirring and mixing the sodium dodecyl benzene sulfonate modified zeolite with citric acid and deionized water according to a mass ratio of 1:0.2:6 to obtain a mixed solution; placing the mixed solution in a reaction kettle and sealing the reaction kettle, then heating to 90℃ and constant temperature stirring for 5h, then cooling to room temperature, filtering, washing and drying to obtain carboxylated zeolite.

[0063] (3) Carboxylated zeolite and aminopolysilsesquioxane were added into tetrahydrofuran, stirred and mixed, then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added, stirred and mixed, then warmed to 70℃ and stirred for 2h, the mass ratio of carboxylated zeolite, aminopolysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran was 1:0.3:0.05:0.06:13; then cooled to room temperature, filtered, washed and dried to obtain the polysilsesquioxane modified zeolite.

[0064] (4) 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 23 parts of polysilsesquioxane modified zeolite and 0.3 parts of antioxidant 1010 were mixed to obtain a mixture, and the mixture was subjected to melt blending, extrusion and granulation in a twin-screw extruder to obtain the zeolite modified polypropylene material. The temperature of each zone of the twin-screw extruder was as follows: Zone 1: 175℃; Zone 2: 185℃; Zone 3: 195℃; Zone 4: 205℃; Zone 5: 205℃; Zone 6: 215℃; Zone 7: 215℃; and die head: 215℃.

[0065] Comparative Example 1

[0066] Different from Example 6, the step (2) of the preparation method of the zeolite modified polypropylene material in the present comparative example included the following steps: the pretreated zeolite was stirred and mixed with citric acid and deionized water at a mass ratio of 1:0.2:6 to obtain a mixed solution; the mixed solution was placed in a reaction kettle and the reaction kettle was closed, then warmed to 90℃ and stirred for 5h, then cooled to room temperature, filtered, washed and dried to obtain the carboxylated zeolite.

[0067] The remaining steps (1), (3) and (4) were basically the same as those of Example 6.

[0068] Comparative Example 2

[0069] Different from Example 6, the step (2) of the preparation method of the zeolite modified polypropylene material in the present comparative example included the following steps: pretreated zeolite powder was added into a 5% sodium dodecyl benzene sulfonate aqueous solution, the mass ratio of pretreated zeolite powder to sodium dodecyl benzene sulfonate aqueous solution was 1:12, warmed to 60℃ and stirred for 12h, then cooled to room temperature, filtered, washed and dried to obtain sodium dodecyl benzene sulfonate modified zeolite; then the sodium dodecyl benzene sulfonate modified zeolite was stirred and mixed with citric acid and deionized water at a mass ratio of 1:0.2:6 to obtain a mixed solution; the mixed solution was warmed to 60℃ and stirred for 10h (without hydrothermal reaction), then cooled to room temperature, filtered, washed and dried to obtain the carboxylated zeolite.

[0070] The remaining steps (1), (3), and (4) are basically the same as those in Example 6.

[0071] Comparative Example 3:

[0072] The preparation method of the zeolite modified polypropylene material in the present comparative example comprises the following steps:

[0073] (1) Zeolite powder with a particle size of 150-200 mesh and aminocage polysilsesquioxane were added to tetrahydrofuran, stirred and mixed, then 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide were added, stirred and mixed, then heated to 70°C for constant temperature stirring for 2h, and the mass ratio of zeolite powder, aminocage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, N-hydroxysuccinimide, and tetrahydrofuran was 1:0.3:0.05:0.06:13; then cooled to room temperature, filtered, washed, and dried to obtain cage polysilsesquioxane modified zeolite.

[0074] (2) 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 23 parts of cage polysilsesquioxane modified zeolite, and 0.3 parts of antioxidant 1010 were mixed to obtain a mixture, and then the mixture was 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 was as follows: 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; and die head: 215°C.

[0075] Comparative Example 4:

[0076] The preparation method of the zeolite modified polypropylene material in the present comparative example comprises the following steps:

[0077] (1) Zeolite powder with a particle size of 150-200 mesh was placed in a calcination furnace, heated to 550°C at a rate of 15°C / min, and calcined for 50 min, then cooled to room temperature with the furnace to obtain pretreated zeolite powder.

[0078] (2) Pretreated zeolite powder was added to a 5% sodium dodecylbenzenesulfonate aqueous solution, the mass ratio of pretreated zeolite powder to sodium dodecylbenzenesulfonate aqueous solution was 1:12, heated to 60°C for constant temperature stirring for 12h, then cooled to room temperature, filtered, washed, and dried to obtain sodium dodecylbenzenesulfonate modified zeolite.

[0079] (3) 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 23 parts of sodium dodecyl benzene sulfonate modified zeolite, 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 as follows: 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; and die head: 215°C.

[0080] Comparative Example 5:

[0081] The preparation method of the zeolite modified polypropylene material in this comparative example includes the following steps:

[0082] 100 parts of polypropylene, 8 parts of maleic anhydride grafted polypropylene, 23 parts of zeolite powder (particle size of 150-200 mesh), 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 as follows: 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; and die head: 215°C.

[0083] Performance test:

[0084] The zeolite modified polypropylene materials in Examples 1-6 and Comparative Examples 1-5 are injection molded into tensile samples (length 150 mm x width 10 mm x thickness 4 mm) and impact samples (length 80 mm x width 10 mm x thickness 4 mm, with a notch remaining width of 8 mm) in an injection molding machine. The tensile strength test is performed according to the method in GB / T1040.1-2018 "Determination of tensile properties of plastics", and the notched impact strength test is performed according to the method in GB / T1843-2008 "Determination of Izod impact strength of plastics".

[0085] Table 1: Tensile strength and elongation at break test results

[0086]

[0087] As can be seen from Table 1, the zeolite modified polypropylene materials prepared by the cage-type polysilsesquioxane modified zeolite in the examples all have high tensile strength and impact strength. As can be seen from the comparison between Example 6 and Comparative Example 5, the modification of the zeolite by the method of the present application can significantly improve the strength and impact resistance of the polypropylene material.

[0088] It can be seen from the comparison between Example 6 and Comparative Example 1 that, if the zeolite is not modified by sodium dodecyl benzene sulfonate, the strength and impact resistance of the zeolite-modified polypropylene material will decrease. It can be seen from the comparison between Example 6 and Comparative Example 2 that, if the hydrothermal reaction is not performed in the preparation of the carboxylated zeolite, the strength and impact resistance of the zeolite-modified polypropylene material will decrease.

[0089] It can be seen from the comparison between Example 6 and Comparative Example 3 that, if the zeolite is not modified by sodium dodecyl benzene sulfonate and carboxylation, or the zeolite-modified polypropylene material is directly prepared by modifying the zeolite with sodium dodecyl benzene sulfonate, the strength and impact resistance of the zeolite-modified polypropylene material will significantly decrease.

[0090] The above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can be modified, or some of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A process for the preparation of a zeolite-modified polypropylene material, characterized in that, It comprises the following steps: (1) The zeolite powder is calcined to obtain pretreated zeolite powder; (2) The pretreated zeolite powder is added to a sodium dodecyl benzene sulfonate aqueous solution, heated to 60-70℃ for constant temperature stirring, then cooled to room temperature, filtered, washed and dried to obtain sodium dodecyl benzene sulfonate modified zeolite; The sodium dodecyl benzene sulfonate modified zeolite is mixed with citric acid and deionized water to obtain a mixed solution; The mixed solution is placed in a reaction kettle and the reaction kettle is closed, then heated to 90-95℃ for constant temperature stirring, then cooled to room temperature, filtered, washed and dried to obtain carboxylated zeolite; (3) The carboxylated zeolite and aminocage polysilsesquioxane are added to tetrahydrofuran, stirred and mixed, then 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride and N-hydroxysuccinimide are added, stirred and mixed, then heated to 55-70℃ for constant temperature stirring; Then cooled to room temperature, filtered, washed and dried to obtain cage polysilsesquioxane modified zeolite; The mass ratio of the carboxylated zeolite, aminocage polysilsesquioxane, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, N-hydroxysuccinimide and tetrahydrofuran is 1:0.3-0.6:0.05-0.09:0.04-0.06:11-15; (4) The polypropylene, maleic anhydride grafted polypropylene, cage polysilsesquioxane modified zeolite and antioxidant are mixed to obtain a mixture, then the mixture is placed in a twin-screw extruder for melt blending, extrusion and granulation to obtain the zeolite modified polypropylene material; The zeolite modified polypropylene material comprises the following raw materials by weight: polypropylene 100 parts, maleic anhydride grafted polypropylene 6-12 parts, cage polysilsesquioxane modified zeolite 18-25 parts, and antioxidant 0.2-0.5 parts.

2. The process for the preparation of a zeolite-modified polypropylene material according to claim 1, characterized in that, The step (1) specifically comprises the following steps: the zeolite powder is placed in a calcining furnace, heated to 520-580℃ at a rate of 10-18℃ / min, and calcined for 40-60min, then cooled to room temperature in the furnace to obtain pretreated zeolite powder.

3. The process for the preparation of a 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 of producing a zeolite-modified polypropylene material according to claim 1, characterized by, In step (2), the mass fraction of the sodium dodecyl benzene sulfonate aqueous solution is 4-9%, and the mass ratio of the pretreated zeolite powder to the sodium dodecyl benzene sulfonate aqueous solution is 1:12-18; The mass ratio of the sodium dodecyl benzene sulfonate modified zeolite, citric acid and deionized water is 1:0.2-0.3:4.5-6.

5. The method of producing a zeolite-modified polypropylene material according to claim 1, characterized by, In step (2), the time for constant temperature stirring at 60-70℃ is 10-15h, and the time for constant temperature stirring at 90-95℃ is 4.5-7h. In step (3), the time for constant temperature stirring at 55-70℃ is 2-3h.

6. The method of producing a zeolite-modified polypropylene material according to claim 1, characterized by, The antioxidant is one of antioxidant 1010 and antioxidant 1076 or a combination of the two.

7. The method of producing a zeolite-modified polypropylene material according to claim 1, characterized by, The temperature of each zone of the twin-screw extruder is as follows: 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.

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