Spraying-free polypropylene composite material and preparation method thereof

Abstract

The invention discloses a spraying-free polypropylene composite material and a preparation method thereof. The spraying-free polypropylene composite material is prepared from the following components in parts by weight: 70-90 parts of polypropylene resin, 3-5 parts of modified metal powder, 1-3 parts of a compatilizer, 10-30 parts of talcum powder, 0.1-0.5 part of a lubricant and 0.3-1 part of other auxiliaries. The silver powder is coated with the COFs material, the COFs material is utilized to perform in-situ growth on the surface of the silver powder so as to coat the silver powder, and meanwhile, the porous structure of the COFs material is utilized to promote pre-dispersion of the silver powder. In addition, a coupling agent is grafted in the growth process of the COFs material, so that the material is endowed with surface activity, good compatibility between the modified silver powder and the polypropylene material is ensured, and dispersion of the modified silver powder is facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material modification, and specifically relates to a spray-free polypropylene composite material and a preparation method thereof. Background Art

[0002] As an important general polymer material, polypropylene (PP) is widely used in many industries such as the automotive industry, home appliance manufacturing, and mechanical fields due to its low density, easy processing, excellent mechanical properties, and good chemical corrosion resistance. However, with the increasingly strict environmental protection requirements and the continuous improvement of consumers' requirements for the appearance quality of products, traditional polypropylene materials have gradually revealed some deficiencies in certain application fields.

[0003] Traditional polypropylene materials usually need to be subjected to surface treatment processes such as painting or electroplating to improve their appearance effects to meet the requirements for gloss and metallic texture of automotive interior and exterior trims, home appliance exterior parts, etc. However, these surface treatment processes not only increase production costs but also bring environmental pollution problems.

[0004] Spray-free PP materials are often used to prepare automotive interior and exterior trims and home appliance exterior parts due to their good appearance effects and high gloss. Spray-free is achieved by adding metal powder to the plastic raw material and directly injection molding to improve the performance of the product and present a spray appearance effect. However, in existing spray-free polypropylene materials, after adding metal powder, due to the poor dispersion of the metal powder in the polypropylene matrix, it is easy to agglomerate, affecting the appearance and mechanical properties of the final product. Summary of the Invention

[0005] In view of this, the present invention provides a spray-free polypropylene composite material and a preparation method thereof to solve the problems raised in the above background art. By adding a low content of modified metal powder, the polypropylene composite material is given a good metallic appearance effect and high mechanical properties are maintained, solving the deficiencies in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] In a first aspect, the present invention discloses a spray-free polypropylene composite material, which is prepared from the following components according to parts by weight:

[0008]

[0009]

[0010] As a further aspect of the present invention: The metal powder in the modified metal powder is at least one of gold powder, silver powder, aluminum powder, and copper powder.

[0011] As a further aspect of the present invention: The preparation method of the modified metal powder is:

[0012] Mix 2,5-dimethylterephthalohydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene and n-butanol evenly, then add acetic acid and heat to 50-60 °C, react for 3-5 min to obtain COFs material. Add metal powder and coupling agent thereto, fully disperse and then evacuate, and heat for reaction; after cooling to room temperature, filter to obtain modified metal powder.

[0013] As a further scheme of the present invention: the mass ratio of 2,5-dimethylterephthalohydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol, acetic acid, metal powder and coupling agent is 67:79:3:2:60:(50-100):(0.1-1).

[0014] As a further scheme of the present invention: the heating reaction is specifically carried out at 110-130 °C for 70-80 h.

[0015] As a further scheme of the present invention: the coupling agent is one of silane coupling agent, titanate coupling agent, aluminate coupling agent, phosphate coupling agent.

[0016] As a further scheme of the present invention: the compatibilizer is at least one of PP-g-MAH and POE-g-MAH.

[0017] As a further scheme of the present invention: the lubricant is a non-polar lubricant;

[0018] Preferably, the non-polar lubricant is polyethylene wax or polypropylene wax.

[0019] As a further scheme of the present invention: the other additives are at least one of antioxidant, auxiliary antioxidant, light absorber, light stabilizer.

[0020] In the second aspect, the present invention discloses a preparation method of the above spray-free polypropylene composite material, including the following steps:

[0021] Weigh each component according to parts by weight and mix evenly to obtain a mixture;

[0022] Add the mixture to an extruder, and after melting, extruding, granulating, cooling and drying, the spray-free polypropylene composite material is obtained;

[0023] The temperatures of each zone of the extruder are: zone 1 at 160 °C, zone 2 at 180 °C, zone 3 at 190 °C, zone 4 at 200 °C, zone 5 at 210 °C, zone 6 at 220 °C, and the head at 210 °C; the screw speed is 500 r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06 MPa.

[0024] Compared with the prior art, the beneficial effects of the present invention are:

[0025] 1. The present invention coats silver powder with COFs materials, in-situ grows the COFs materials on the surface of the silver powder to form a coating, and promotes the pre-dispersion of the silver powder by using the porous structure of the COFs materials. In addition, a coupling agent is grafted during the growth of the COFs materials to endow the material surface with activity, ensuring good compatibility between the modified silver powder and the polypropylene material, which is beneficial to the dispersion of the modified silver powder.

[0026] 2. For a spray-free polypropylene composite material provided by the present invention, when a compatibilizer and a lubricant are simultaneously added to the formulation, can it further promote the dispersion of the modified silver powder during processing?

[0027] 3. The spray-free polypropylene composite material prepared by the present invention can be recycled and reused, meeting the development requirements of green and recyclable materials for household appliances and automobiles. Specific Embodiments

[0028] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below in conjunction with specific embodiments. However, the present invention can be implemented 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 invention more thorough and comprehensive.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0030] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0031] Polypropylene homopolymer (PP-H), grade 012, density 0.9 g / cm 3 , melt index 1.2 g / 10 min (temperature 230 °C, load 2.16 Kg), manufacturer: Shandong Wusheng Natural Gas Chemical Co., Ltd.

[0032] The metal powder selected is silver powder, with a silver-white color and metallic luster, micron size 300 - 10,000 mesh, manufacturer: Hebei Wenlun Metal Materials Co., Ltd.

[0033] Silane coupling agent KH550, manufacturer: Shandong Yuanjin New Materials Co., Ltd.;

[0034] The preparation method of COFs materials is as follows: Weigh 670 g of 2,5-dimethylterephthalohydrazide, 790 g of (4-formylphenyl)-1,3,5-triazine, 30 g of o-dichlorobenzene and 20 g of n-butanol, mix them evenly, add 60 g of acetic acid (concentration: 6 mol / L), heat up to 60 °C, react for 3 - 5 minutes to obtain COFs materials.

[0035] The compatibilizer is maleic anhydride grafted polypropylene, grade: Sabic 350K, grafting rate 0.7 - 0.9%, manufacturer: Dongguan Shenghao Plastic Raw Materials Co., Ltd.

[0036] Talc powder, industrial grade, 600 mesh, manufacturer: Lingshou Erping Mineral Products Processing Factory.

[0037] The lubricant is polyethylene wax, grade Q-112PE wax, manufacturer: Wuhan Xindongyi Chemical Co., Ltd.

[0038] Other additives are mixed by a master antioxidant, a co-antioxidant, a light absorber and a light stabilizer in a mass ratio of 1:1:1:1. The master antioxidant grade is Irganox 565, manufacturer: BASF Germany. The co-antioxidant grade is AN 168, manufacturer: Qingdao Deda Special Chemicals Group. The light absorber grade is Chiguard 5050, manufacturer: Qitai Co., Ltd. The light stabilizer grade is LA-52, manufacturer: Adeka (China) Investment Co., Ltd.

[0039] All materials are commercially available conventional products.

[0040] It can be understood that the above raw materials and reagents are only examples of some specific embodiments of the present invention to make the technical solution of the present invention clearer, and do not represent that the present invention can only use the above reagents. Specifically, it shall be subject to the scope in the claims. In addition, the "parts" mentioned in the examples and comparative examples refer to weight parts unless otherwise specified.

[0041] Any range recorded in the present invention includes the end values and any numerical values between the end values, as well as any sub-ranges constituted by any numerical values between the end values or the end values.

[0042] Example 1

[0043] Prepare modified metal powder: Weigh 670 g of 2,5-dimethylterephthalohydrazide, 790 g of (4-formylphenyl)-1,3,5-triazine, 30 g of o-dichlorobenzene and 20 g of n-butanol, mix them evenly, add 60 g of acetic acid (concentration: 6 mol / L), heat up to 60 °C, react for 3 - 5 minutes, then add 1000 g of metal powder and 10 g of KH550 coupling agent, put them together into a rotary vacuum drying oven, evacuate, rotate and heat to 120 °C, and react at 120 °C for 72 h, then cool to room temperature to obtain modified metal powder;

[0044] Weigh 90 parts of polypropylene resin, 5 parts of modified metal powder, 2 parts of compatibilizer, 10 parts of talc powder, 0.5 part of lubricant, and 1 part of other additives. After mixing evenly, put them into a twin-screw extruder. After melting, extrusion, granulation, cooling, and drying, a spray-free polypropylene composite material is obtained. Among them, the barrel temperature is 160 °C in zone 1, 220 °C in zone 2, 220 °C in zone 3, 230 °C in zone 4, 230 °C in zone 5, 230 °C in zone 6, and 220 °C at the die head. The screw speed is 500 r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06 MPa.

[0045] Example 2

[0046] Prepare the modified metal powder: Weigh 670 g of 2,5-dimethylterephthalohydrazide, 790 g of (4-formylphenyl)-1,3,5-triazine, 30 g of o-dichlorobenzene, and 20 g of n-butanol, mix them evenly, add 60 g of acetic acid (concentration 6 mol / L), heat up to 60 °C, react for 3 - 5 minutes, then add 500 g of metal powder and 1 g of KH550 coupling agent; put them together into a rotary vacuum drying oven, evacuate, rotate and heat to 120 °C, and react at 120 °C for 72 h, then cool to room temperature to obtain the modified metal powder;

[0047] Weigh 90 parts of polypropylene resin, 4 parts of modified metal powder, 2 parts of compatibilizer, 10 parts of talc powder, 0.5 part of lubricant, and 1 part of other additives. After mixing evenly, put them into a twin-screw extruder. After melting, extrusion, granulation, cooling, and drying, a spray-free polypropylene composite material is obtained. Among them, the barrel temperature is 160 °C in zone 1, 220 °C in zone 2, 220 °C in zone 3, 230 °C in zone 4, 230 °C in zone 5, 230 °C in zone 6, and 220 °C at the die head. The screw speed is 500 r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06 MPa.

[0048] Example 3

[0049] Prepare the modified metal powder: Weigh 670 g of 2,5-dimethylterephthalohydrazide, 790 g of (4-formylphenyl)-1,3,5-triazine, 30 g of o-dichlorobenzene, and 20 g of n-butanol, mix them evenly, add 60 g of acetic acid (concentration 6 mol / L), heat up to 60 °C, react for 3 - 5 minutes, then add 800 g of metal powder and 8 g of KH550 coupling agent; put them together into a rotary vacuum drying oven, evacuate, rotate and heat to 120 °C, and react at 120 °C for 72 h, then cool to room temperature to obtain the modified metal powder;

[0050] Weigh 90 parts of polypropylene resin, 3 parts of modified metal powder, 2 parts of compatibilizer, 10 parts of talc powder, 0.5 part of lubricant, and 1 part of other additives. After mixing evenly, put them into a twin-screw extruder, and obtain the spray-free polypropylene composite material through melting, extrusion, pelletizing, cooling, and drying. Among them, the barrel temperature is 160 °C in zone 1, 220 °C in zone 2, 220 °C in zone 3, 230 °C in zone 4, 230 °C in zone 5, 230 °C in zone 6, and 220 °C at the die head. The screw speed is 500 r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06 MPa.

[0051] Comparative Example 1

[0052] Weigh 90 parts of polypropylene resin, 10 parts of talc powder, 2 parts of compatibilizer, 0.5 part of lubricant, and 1 part of other additives. After mixing evenly, put them into a twin-screw extruder, and obtain the spray-free polypropylene composite material through melting, extrusion, pelletizing, cooling, and drying. Among them, the barrel temperature is 160 °C in zone 1, 220 °C in zone 2, 220 °C in zone 3, 230 °C in zone 4, 230 °C in zone 5, 230 °C in zone 6, and 220 °C at the die head. The screw speed is 500 r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06 MPa.

[0053] Comparative Example 2

[0054] Weigh 90 parts of polypropylene resin, 3 parts of silver powder, 2 parts of compatibilizer, 10 parts of talc powder, 0.5 part of lubricant, and 1 part of other additives. After mixing evenly, put them into a twin-screw extruder, and obtain the spray-free polypropylene composite material through melting, extrusion, pelletizing, cooling, and drying. Among them, the barrel temperature is 160 °C in zone 1, 220 °C in zone 2, 220 °C in zone 3, 230 °C in zone 4, 230 °C in zone 5, 230 °C in zone 6, and 220 °C at the die head. The screw speed is 500 r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06 MPa.

[0055] Comparative Example 3

[0056] Weigh 90 parts of polypropylene resin, 5 parts of silver powder, 2 parts of compatibilizer, 10 parts of talc powder, 0.5 part of lubricant, and 1 part of other additives. After mixing evenly, put them into a twin-screw extruder, and obtain the spray-free polypropylene composite material through melting, extrusion, pelletizing, cooling, and drying. Among them, the barrel temperature is 160 °C in zone 1, 220 °C in zone 2, 220 °C in zone 3, 230 °C in zone 4, 230 °C in zone 5, 230 °C in zone 6, and 220 °C at the die head. The screw speed is 500 r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06 MPa.

[0057] Test Example

[0058] The polypropylene composites prepared in the examples and comparative examples were respectively put into an injection molding machine to prepare standard specimens. The barrel temperature of the injection molding machine was 220 °C and the mold temperature was 60 °C. Performance tests were carried out on each standard specimen, and the test items and results are shown in Table 1.

[0059] Table 1

[0060]

[0061]

[0062] It can be seen from Table 1 that the talc-filled polypropylene in Comparative Example 1 has no metallic luster and a low gloss. After adding 3 parts of silver powder in Comparative Example 2, the composite material has metallic luster, but the gloss is low, and the tensile strength, flexural strength and impact strength of the material all decrease. In Comparative Example 3, 5 parts of silver powder were added, the composite material has metallic luster and the gloss is improved, but the tensile strength, flexural strength and impact strength of the material all further decrease. After adding modified silver powder, compatibilizer and lubricant in Examples 1 to 3, the composite material has metallic luster and good gloss. At the same time, the material also has high tensile strength, flexural strength and impact strength, greatly expanding the application fields of the spray-free polypropylene composite material, which has important popularization significance.

[0063] Although this specification is described according to the implementation manners, not each implementation manner only contains an independent technical solution. This narrative manner of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other implementation manners that can be understood by those skilled in the art.

[0064] Therefore, the above are only the preferred embodiments of the present application, and are not used to limit the scope of implementation of the present application; that is, all equivalent transformations made according to the scope of the claims of the present application are within the protection scope of the claims of the present application.

Claims

1. A spray-free polypropylene composite material, characterized in that: It is prepared from the following components in parts by weight:

2. The spray-free polypropylene composite material according to claim 1, characterized in that: The metal powder in the modified metal powder is at least one of gold powder, silver powder, aluminum powder and copper powder.

3. The spray-free polypropylene composite material according to claim 1, characterized in that: The preparation method of the modified metal powder is: 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene and n-butanol are mixed evenly, and then acetic acid is added and heated to 50-60°C, and the reaction is carried out for 3-5 minutes to obtain COFs material, metal powder and coupling agent are added thereto, and after being fully dispersed, vacuum is evacuated and heated for reaction; after cooling to room temperature, it is filtered to obtain modified metal powder.

4. The spray-free polypropylene composite material according to claim 3, characterized in that: The mass ratio of the 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol, acetic acid, metal powder and coupling agent is 67:79:3:2:60:(50-100):(0.1-1).

5. The spray-free polypropylene composite material according to claim 3, characterized in that: The heating reaction is specifically carried out at 110-130° C. for 70-80 hours.

6. The spray-free polypropylene composite material according to claim 3, characterized in that: The coupling agent is one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a phosphate coupling agent.

7. The spray-free polypropylene composite material according to claim 1, characterized in that: The compatibilizer is at least one of PP-g-MAH and POE-g-MAH.

8. The spray-free polypropylene composite material according to claim 1, characterized in that: The lubricant is a non-polar lubricant; the non-polar lubricant is polyethylene wax or polypropylene wax.

9. The spray-free polypropylene composite material according to claim 1, characterized in that: The other auxiliary agent is at least one of an antioxidant, an auxiliary antioxidant, a light absorber, and a light stabilizer.

10. The method for preparing the spray-free polypropylene composite material according to any one of claims 1 to 9, characterized in that: The following steps are involved: Weigh each component according to weight and mix them evenly to obtain a mixture; The mixed material is added into an extruder, and after melting, extrusion, granulation, cooling and drying, a spray-free polypropylene composite material is obtained; The temperatures of each zone of the extruder are: 160°C for zone 1, 180°C for zone 2, 190°C for zone 3, 200°C for zone 4, 210°C for zone 5, 220°C for zone 6, and 210°C for die head; the screw speed is 500r / min, the melt pressure is 1.0MPa, and the vacuum degree is -0.06MPa.

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