Low odor polypropylene composite material, and preparation method and application thereof

Abstract

The application belongs to the technical field of polymer composites, and particularly relates to a low-odor polypropylene composite material and a preparation method and application thereof. The low-odor polypropylene composite material comprises a PP resin, a filler, an antioxidant, a lubricant and a deodorizing agent COF@ZnO composite material in components. The COF material has a porous structure and regular channels, shows high porosity and high surface area, and is rich in benzene ring structures to adsorb benzene series and other small molecular substances generated in the melting extrusion of polypropylene through conjugation and physical action. The nano ZnO is dispersed on the surface of the COF material to play a photocatalytic role to degrade VOCs substances, and meanwhile, the COF skeleton can also accelerate the transmission of electrons to promote the catalytic action, so that the odor is improved through the synergistic action, and the problem of the generation of volatile unpleasant gas in the polypropylene material in the prior art is solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer composite materials, and particularly relates to a low-odor polypropylene composite material and a preparation method and application thereof. BACKGROUND

[0002] With the progress of industrial technology, the engineering modification technology of polypropylene (PP) material has developed rapidly. A certain amount of inorganic fillers and organic components are added in the extrusion granulation process to realize high performance of PP to meet the requirements of automobile parts. At present, modified PP parts have been widely used in various parts of the vehicle, including instrument tables, storage boxes, interior panels, etc., showing a series of advantages such as light weight, high strength, aging resistance, corrosion resistance, etc. However, in practical application, such interior parts usually show a certain volatility, producing unpleasant gas in the vehicle, deteriorating the air quality in the vehicle, and adversely affecting the user's experience and health.

[0003] At present, the solution to this problem is usually to add a vacuum extraction device or post-treatment baking in the extrusion granulation process, using vacuum or high temperature to remove small molecular odor substances, which requires additional equipment, has high cost, and has poor effect. In addition, porous adsorbents such as activated carbon, silicates, etc. are added to the formula to adsorb volatile substances to solve the odor problem, but the efficiency of a single adsorbent is limited, the effect is weak, the odor improvement is not obvious, and too much addition may affect the mechanical properties. Therefore, it is still necessary to research and develop a low-odor polypropylene composite material for vehicles SUMMARY

[0004] The purpose of the present application is to provide a low-odor polypropylene composite material to solve the problem of volatile unpleasant gas in the polypropylene material in the background art.

[0005] To achieve the above purpose, the following technical solution is adopted: a low-odor polypropylene composite material, consisting of the following components by weight:

[0006]

[0007]

[0008] The odor removal agent is a COF@ZnO composite material.

[0009] As a further improvement of the low-odor polypropylene composite material:

[0010] Preferably, the filler is one or a combination of two or more of talc, calcium carbonate, barium sulfate, wollastonite, mica.

[0011] Preferably, the lubricant is one or a combination of two or more of silicone, stearate, erucic acid amide.

[0012] Preferably, the synthesis steps of the COF@ZnO composite material are as follows:

[0013] S1, dissolve 1, 3, 5-tri (4-aminophenyl) benzene, p-xylylene in 1, 4-dioxane and 1, 3, 5-trimethylbenzene mixed solvent, then transfer the whole solution system to the reaction kettle, heat to 110-120℃, keep for 48-72h, then the reaction product is centrifuged, washed, soaked, centrifuged and dried, and the COF material is obtained;

[0014] S2, disperse ZnO nanoparticles in anhydrous methanol, the dispersion concentration is 0.2-0.6g / ml, stir to form a uniform suspension, then add COF material, dry in an oven at 110-120℃ for 12-24h after the ethanol is completely volatilized, and obtain the COF@ZnO composite material.

[0015] Preferably, the mass ratio of 1, 3, 5-tri (4-aminophenyl) benzene, p-xylylene, 1, 4-dioxane and 1, 3, 5-trimethylbenzene in step S1 is 6:3:500:100; the mass ratio of the COF material and ZnO nanoparticles in step S2 is 2:1.

[0016] Preferably, the reaction product in step S2 is washed and soaked in acetone and tetrahydrofuran after centrifugation.

[0017] The second object of the application is to provide a preparation method of the low-odor polypropylene composite material as described in any one of the above, comprising the following steps:

[0018] a, the PP resin, the filler, the antioxidant, the lubricant and the odor removal agent are weighed according to the proportion, stirred and mixed at a speed of 300-500r / min for 5-10min to obtain uniformly mixed materials;

[0019] b, the uniformly mixed materials are put into a parallel twin-screw extruder for melting, extrusion and granulation to prepare the polypropylene composite material.

[0020] The preparation method of the low-odor polypropylene composite material is further improved:

[0021] Preferably, the barrel temperature of the parallel twin-screw extruder is 180-220℃, the screw rotation speed is 400-600r / min, the melt pressure is 1.5-2.5MPa, and the vacuum degree is-0.06--0.1MPa.

[0022] The third object of the application is to provide an application of the low-odor polypropylene composite material as described in any one of the above to automobile interior parts.

[0023] The beneficial effects of the present application compared with the prior art are:

[0024] 1) The present application provides a low odor polypropylene composite material, which comprises PP resin, filler, antioxidant, lubricant and odor removal agent COF@ZnO composite material in components; by reasonable formula design, a low odor polypropylene composite material is prepared by adding an odor removal agent in the polypropylene composite material formula. The odor removal agent is COF@ZnO composite material, the COF material has a porous structure and regular channels, showing high porosity and high surface area, and is rich in benzene ring structure, to adsorb benzene and other small molecular substances generated during the melt extrusion of polypropylene by conjugation and physical action; nano ZnO is dispersed on the surface of the COF material, which can play a photocatalytic role to degrade VOCs substances, and the COF skeleton can also accelerate the transfer of electrons to promote catalysis, and the two realize the improvement of odor by synergistic effect.

[0025] 2) The present application uses COF@ZnO composite material as an odor removal agent, which is prepared by a solvent evaporation method. The technical principle of this method is that organic monomers, 3,5-tris(4-aminophenyl)benzene and terephthaldehyde, form a COF skeleton through Schiff base reaction, and the unreacted amino groups and the hydroxyl groups on the surface of zinc oxide form hydrogen bonds, which are tightly combined and stable in structure.

[0026] 3) The present application also provides a preparation method of a low odor polypropylene composite material. The preparation method is simple in process, can be mass-produced, and the odor of the extruded particles or parts is obviously improved. DETAILED DESCRIPTION

[0027] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to specific embodiments. However, the present application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0029] Table 1: The added weight parts of each component in examples 1-5 and comparative examples 1-2

[0030]

[0031] Example 1

[0032] The present embodiment provides a preparation method of a low odor polypropylene composite material, which specifically comprises the following steps:

[0033] (1) 0.6 g of 1,3,5-tris(4-aminophenyl)benzene and 0.3 g of p-phenylenediformaldehyde were dissolved in 50 g of 1,4-dioxane and 10 g of 1,3,5-trimethylbenzene mixed solvent, and then the whole solution system was transferred to a reaction kettle, heated to 120°C, kept for 72 h, and then centrifuged, washed with acetone, soaked in tetrahydrofuran, centrifuged, and dried to obtain a COF material.

[0034] 20 g of ZnO nanoparticles (particle size of 10-55 nm, structure of hexagonal wurtzite structure) were dispersed in 50 mL of anhydrous methanol, the dispersion concentration was 0.4 g / ml, and after stirring for 1 h, a uniform suspension was formed. 10 g of COF material was added to the above solution, and after the ethanol was completely volatilized, the COF@ZnO composite material was obtained by drying at 110°C in an oven for 24 h.

[0035] (2) The PP resin (MK51140T, Zhongsha Tianjin), filler, antioxidant, lubricant and odor removal agent were weighed according to the ratio in Table 1 and mixed at high speed to obtain a uniformly mixed material.

[0036] (3) The uniformly mixed material was put into a parallel twin-screw extruder for melting, extrusion and granulation to prepare a polypropylene composite material. The barrel temperature of the parallel twin-screw extruder was 180°C, the screw rotation speed was 400 r / min, the melt pressure was 2.0 MPa, and the vacuum degree was -0.1 MPa.

[0037] The filler is talc, the lubricant is calcium stearate, the antioxidant is a complex of hindered phenol and phosphite, specifically 1010 and 168, and the odor removal agent is COF@ZnO composite material.

[0038] Example 2

[0039] The present embodiment provides a preparation method of a low-odor polypropylene composite material, which specifically comprises the following steps:

[0040] (1) 0.6 g of 1,3,5-tris(4-aminophenyl)benzene and 0.3 g of p-phenylenediformaldehyde were dissolved in 50 g of 1,4-dioxane and 10 g of 1,3,5-trimethylbenzene mixed solvent, and then the whole solution system was transferred to a reaction kettle, heated to 120°C, kept for 72 h, and then centrifuged, washed with acetone, soaked in tetrahydrofuran, centrifuged, and dried to obtain a COF material.

[0041] 20g of ZnO nanoparticles (particle size of 10-55nm, structure of hexagonal wurtzite structure) were dispersed in 50mL of anhydrous methanol, the dispersion concentration was 0.4g / ml, after stirring for 1h, a uniform suspension was formed, 10g of COF material was added to the above solution, and finally after the ethanol was completely volatilized, it was dried in an oven at 110℃ for 24h to obtain the COF@ZnO composite material.

[0042] (2) The PP resin (MK51140T, Zhongsha Tianjin), filler, antioxidant, lubricant and odor removal agent were weighed according to the ratio in Table 1 and high-speed mixed to obtain a uniformly mixed material;

[0043] (3) The uniformly mixed material was put into a parallel twin-screw extruder for melting and extrusion granulation to prepare a polypropylene composite material; the barrel temperature of the parallel twin-screw extruder was 180℃, the screw rotation speed was 400r / min, the melt pressure was 2.0MPa, and the vacuum degree was-0.1MPa.

[0044] The filler is talc, the lubricant is calcium stearate, the antioxidant is a complex of hindered phenol and phosphite, specifically 1010 and 168, and the odor removal agent is COF@ZnO composite material.

[0045] Example 3

[0046] The embodiment provides a preparation method of a low-odor polypropylene composite material, which specifically comprises the following steps:

[0047] (1) 6g of 1,3,5-tris(4-aminophenyl)benzene and 3g of p-phenylenediformaldehyde were dissolved in 500g of 1,4-dioxane and 100g of 1,3,5-trimethylbenzene mixed solvent, then the whole solution system was transferred to a reaction kettle, heated to 120℃, kept for 72h, then centrifuged, washed with acetone, soaked in tetrahydrofuran, centrifuged and dried to obtain a COF material.

[0048] 20g of ZnO nanoparticles (particle size of 10-55nm, structure of hexagonal wurtzite structure) were dispersed in 50mL of anhydrous methanol, the dispersion concentration was 0.4g / ml, after stirring for 1h, a uniform suspension was formed, 10g of COF material was added to the above solution, and finally after the ethanol was completely volatilized, it was dried in an oven at 110℃ for 24h to obtain the COF@ZnO composite material.

[0049] (2) The PP resin (MK51140T, Zhongsha Tianjin), filler, antioxidant, lubricant and odor removal agent were weighed according to the ratio in Table 1 and high-speed mixed to obtain a uniformly mixed material;

[0050] (3) The mixed material is put into a parallel double screw extruder to melt and extrude for granulation to obtain the polypropylene composite material; the barrel temperature of the parallel double screw extruder is 180℃, the screw rotation speed is 400r / min, the melt pressure is 2.0MPa, and the vacuum degree is -0.08MPa.

[0051] The filler is talc, the lubricant is zinc stearate, the antioxidant is a complex of hindered phenol and phosphite, specifically 1076 and 168, and the odor removal agent is COF@ZnO composite.

[0052] Example 4

[0053] The embodiment provides a preparation method of a low-odor polypropylene composite material, and specifically includes the following steps:

[0054] (1) 6g of 1,3,5-tris(4-aminophenyl)benzene and 3g of p-phenylenediformaldehyde are dissolved in 500g of 1,4-dioxane and 100g of mesitylene mixed solvent, and then the whole solution system is transferred to a reaction kettle, heated to 120℃, kept for 72h, and then centrifuged, washed with acetone, soaked in tetrahydrofuran, centrifuged and dried to obtain a COF material.

[0055] 20g of ZnO nanoparticles (particle size of 10-55nm, hexagonal wurtzite structure) are dispersed in 50ml of anhydrous methanol, the dispersion concentration is 0.4g / ml, and after stirring for 1h, a uniform suspension is formed, 10g of the COF material is added to the above solution, and after the ethanol is completely volatilized, the COF@ZnO composite material is obtained by drying at 110℃ in an oven for 24h.

[0056] (2) The PP resin (MK51140T, Zhongsha Tianjin), the filler, the antioxidant, the lubricant and the odor removal agent are weighed according to the ratio in Table 1 and mixed at high speed to obtain a mixed material;

[0057] (3) The mixed material is put into a parallel double screw extruder to melt and extrude for granulation to obtain the polypropylene composite material; the barrel temperature of the parallel double screw extruder is 180℃, the screw rotation speed is 400r / min, the melt pressure is 2.0MPa, and the vacuum degree is -0.08MPa.

[0058] The filler is barium sulfate, the lubricant is calcium stearate, the antioxidant is a complex of hindered phenol and phosphite, specifically 1076 and 168, and the odor removal agent is COF@ZnO composite.

[0059] Comparative Example 1

[0060] The polypropylene composite in the present comparative example is not added odor removal agent, but only added ZnO, other components and component ratio and preparation method are same with example 1.

[0061] Comparative example 2

[0062] The polypropylene composite in the present comparative example is not added odor removal agent, but only added COF material, other components and preparation method are same with example 1.

[0063] Comparative example 3

[0064] The polypropylene composite in the present comparative example is not added odor removal agent, other components and preparation method are same with example 1.

[0065] The polypropylene composite prepared in example 1-4 and comparative example 1-3 is respectively detected according to GB / T standard for tensile strength, bending strength, bending modulus, Izod notched impact strength, odor grade test method refers to German Volkswagen PV3900 test method to test odor grade. The specific method of odor grade test is as follows:

[0066] Put 20g of the above sample into the test vessel, put it into the oven for 2h, the temperature of the oven is set at (80±2)℃, the test vessel must be sealed tightly, after the test vessel is taken out from the oven, it is cooled to 60℃, the cover is slightly removed, the odor is evaluated by professional odor evaluation personnel, the odor grade of the material is divided into 6 levels according to the standard: 1st: no odor, 2nd: odor, but no interfering odor, 3rd: obvious odor, but no interfering odor, 4th: interfering odor, 5th: strong interfering odor, 6th: unbearable odor. The physical test results of example 1-4 and comparative example 1-3 composite are shown in table 2.

[0067] Table 2 physical test results of example 1-4 and comparative example 1-3 composite

[0068]

[0069]

[0070] As can be seen from the test results of Table 2, Examples 1-4 and Comparative Examples 1-3, after adding the odor-removing agent to the formula, the odor grade is obviously increased with the increase of the content of the odor-removing agent, and finally the odor grade of the composite material can reach 3.5, the odor condition is obviously improved, and the basic performance is not decreased, which shows that the introduction of the odor-removing agent has little effect on the particles. In addition, it can also be seen that the odor-removing agent COF@ZnO composite material is better than the single component COF or ZnO in improving the odor, which shows that the two can remove the volatile substances produced in the extrusion and injection molding process through the synergistic effect of adsorption and catalysis, and is helpful to prepare a low-odor polypropylene composite material, and can be applied to automotive interior parts.

[0071] The technical features of the above-described embodiments can be combined in any manner. To make the description concise, all possible combinations of the technical features in the above-described embodiments are not described, but as long as the combinations of the technical features do not contradict, they should be considered within the scope of the present disclosure.

[0072] The above-described embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A low-odor polypropylene composite material, characterized in that: It is composed of the following components in parts by weight: PP resin 70-80 parts, 20-30 parts of filler, 0.2-0.5 parts of antioxidant, 0.2-0.5 parts of lubricant, 0.3-1 part of deodorant; The deodorant is a COF@ZnO composite material, and the synthesis steps are as follows: S1. Dissolve 1,3,5-tris(4-aminophenyl)benzene and terephthalaldehyde in a mixed solvent of 1,4-dioxane and 1,3,5-trimethylbenzene, then transfer the entire solution system to a reactor, heat to 110-120° C., maintain for 48-72 hours, and centrifuge, wash, soak, centrifuge, and dry the reaction product to obtain a COF material; S2. Disperse ZnO nanoparticles in anhydrous methanol at a dispersion concentration of 0.2-0.6 g / ml, stir to form a uniform suspension, then add COF material. After the ethanol evaporates completely, dry in an oven at 110-120° C. for 12-24 hours to obtain a COF@ZnO composite material.

2. The low-odor polypropylene composite material according to claim 1, characterized in that The filler is one or a combination of two or more of talc, calcium carbonate, barium sulfate, wollastonite and mica.

3. The low-odor polypropylene composite material according to claim 1, characterized in that The lubricant is one or a combination of two or more of silicone, stearate and erucamide.

4. The low-odor polypropylene composite material according to claim 1, characterized in that: The ZnO nanoparticles in step S2 have a particle size of 10 to 55 nm and a hexagonal wurtzite structure.

5. The low-odor polypropylene composite material according to claim 1, characterized in that: The mass ratio of 1,3,5-tris(4-aminophenyl)benzene, terephthalaldehyde, 1,4-dioxane and 1,3,5-trimethylbenzene in step S1 is 6:3:500:100; the mass ratio of COF material and ZnO nanoparticles in step S2 is 2:

1.

6. The low-odor polypropylene composite material according to claim 1, characterized in that: In step S2, the reaction product is centrifuged and then washed and soaked in acetone and tetrahydrofuran.

7. A method for preparing the low-odor polypropylene composite material according to any one of claims 1 to 6, characterized in that: The steps include: a. Weigh PP resin, filler, antioxidant, lubricant and deodorant according to the proportion, stir and mix at a speed of 300-500 r / min for 5-10 minutes to obtain a uniform mixture; b. The uniformly mixed materials are put into a parallel twin-screw extruder for melting, extrusion and granulation to obtain a polypropylene composite material.

8. The method for preparing a low-odor polypropylene composite material according to claim 7, characterized in that: The barrel temperature of the parallel twin-screw extruder is 180-220°C, the screw speed is 400-600r / min, the melt pressure is 1.5-2.5MPa, and the vacuum degree is -0.06--0.1MPa.

9. Use of the low-odor polypropylene composite material according to any one of claims 1 to 6 in automobile interior decoration parts.

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