Spraying-free spot-scattering-effect polypropylene composite material as well as preparation method and application thereof

Abstract

The invention relates to a polypropylene composite material with a spraying-free spot scattering effect as well as a preparation method and application of the polypropylene composite material, and belongs to the technical field of compositions of high-molecular compounds. The polypropylene composite material with the spraying-free spot scattering effect is prepared from the following components in parts by weight: 50 to 65 parts of polypropylene resin I, 10 to 20 parts of POE (Polyolefin Elastomer), 3 to 20 parts of compatilizer and 5 to 30 parts of polypropylene resin reclaimed material, the compatilizer is glycidyl methacrylate grafted POE (Polyolefin Elastomer); the polypropylene resin recycled material comprises polypropylene resin II and paint residues, and the particle size D50 of the paint residues is 100-400 [mu] m. The polypropylene composite material not only has good mechanical properties, but also has an excellent scattering appearance effect.

Description

Technical Field

[0001] The present invention relates to the technical field of compositions of polymer compounds, and particularly relates to a spray-free dotting effect polypropylene composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Due to its excellent comprehensive mechanical properties, high heat distortion temperature, chemical corrosion resistance, fatigue resistance and other characteristics, polypropylene is widely used in the fields of automotive industrial parts, daily necessities, packaging films, industrial products, etc. However, with the increase in the production and consumption of polypropylene products, the increasing amount of waste polypropylene materials is likely to cause environmental pollution. At present, there are mainly two ways to recycle waste polypropylene materials. One is to use the heat energy generated by burning waste polypropylene materials for energy supply, and the other is to use it as a raw material resource to be modified and utilized together with other components. For aesthetic requirements, the surfaces of many automotive bumpers and automotive interior parts are generally spray-treated. The paints used for spraying are mainly curable paints (such as thermosetting paints), which have good bonding with the bumper surface, making it difficult to peel off the paint layer in waste bumpers or interior parts. As a result, it is difficult to recycle the painted parts after being scrapped. Summary of the Invention

[0003] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a spray-free dotting effect polypropylene composite material, a preparation method thereof, and an application thereof.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0005] In the first aspect, the present invention provides a spray-free dotting effect polypropylene composite material, which includes the following components by weight: 50 - 65 parts of polypropylene resin I, 10 - 20 parts of POE elastomer, 3 - 20 parts of compatibilizer, and 5 - 30 parts of polypropylene resin recycled material;

[0006] The compatibilizer is glycidyl methacrylate grafted POE (polyolefin elastomer);

[0007] The polypropylene resin recycled material includes polypropylene resin II and paint residues, and the particle size D 50 of the paint residues is 100 - 400 μm.

[0008] The present invention uses glycidyl methacrylate grafted POE as a compatibilizer, combines it with polypropylene resin recycled material containing paint residues, utilizes the epoxy group in the compatibilizer to promote the paint residues to be evenly dispersed in the composite material, and adjusts the particle size distribution of the paint residues to make it present an excellent scattered appearance effect; at the same time, the compatibilizer is also used to enhance the molecular chain entanglement between the polypropylene resin recycled material and the polypropylene resin and the POE elastomer, so that the polypropylene composite material has good mechanical properties.

[0009] It should be noted that the above-mentioned paint residues originate from the curable resin coating (such as from thermosetting paint) that cannot be peeled off on the surface of recycled parts (such as the surface of the bumper), and the mass percentage of paint residues in the recycled polypropylene resin material is 0.1% to 1%; the scattered appearance effect refers to the random generation of a large number of small particles or objects in the scene to simulate the effect of the natural starry sky.

[0010] Optionally, the weight proportion of the polypropylene resin I in the above-mentioned spray-free sprinkling effect polypropylene composite material can be 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 63 parts, and 65 parts, the weight proportion of the POE elastomer can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, and 20 parts, the weight proportion of the compatibilizer can be 3 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, and 20 parts, and the weight proportion of the polypropylene resin recycled material can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, and 30 parts; wherein, the mass percentage of the polypropylene resin I in the spray-free sprinkling effect polypropylene composite material is ≥40%.

[0011] Optionally, the particle size D of the paint residue is 50 The value may be in the range of any one of 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, and 400 μm, or any two of them.

[0012] As a preferred embodiment of the spray-free scattering effect polypropylene composite material of the present invention, the melt mass flow rate of the polypropylene resin I is less than the melt mass flow rate of the polypropylene resin II.

[0013] As a preferred embodiment of the spray-free scattering effect polypropylene composite material of the present invention, it includes the following components in parts by weight: 55 to 60 parts of polypropylene resin I, 12 to 18 parts of POE elastomer, 8 to 12 parts of compatibilizer, and 10 to 20 parts of polypropylene resin recycled material.

[0014] As a preferred embodiment of the spray-free sprinkle effect polypropylene composite material of the present invention, the polypropylene resin I has a melt mass flow rate of 8 to 25 g / 10 min under the conditions of 230 °C and 2.16 kg according to the ISO1133-2011 standard. Optionally, the melt mass flow rate of the polypropylene resin I can specifically be any one of 8 g / 10 min, 10 g / 10 min, 12 g / 10 min, 14 g / 10 min, 16 g / 10 min, 18 g / 10 min, 23 g / 10 min, 25 g / 10 min or the range value of any two of them.

[0015] As a preferred embodiment of the spray-free sprinkle effect polypropylene composite material of the present invention, the polypropylene resin II has a melt mass flow rate of 28 to 50 g / 10 min under the conditions of 230 °C and 2.16 kg according to the ISO1133-2011 standard. Optionally, the melt mass flow rate of the polypropylene resin II can specifically be any one of 28 g / 10 min, 30 g / 10 min, 32 g / 10 min, 34 g / 10 min, 36 g / 10 min, 38 g / 10 min, 40 g / 10 min, 42 g / 10 min, 44 g / 10 min, 46 g / 10 min, 48 g / 10 min, 50 g / 10 min or the range value of any two of them.

[0016] As a preferred embodiment of the spray-free sprinkle effect polypropylene composite material of the present invention, the recycled polypropylene resin is derived from recycled automotive bumpers.

[0017] As a preferred embodiment of the spray-free sprinkle effect polypropylene composite material of the present invention, the POE elastomer includes at least one of ethylene-octene copolymer, ethylene-butene copolymer, and ethylene-propylene copolymer. Optionally, the POE elastomer has a melt mass flow rate of 0.2 to 15 g / 10 min under the conditions of 190 °C and 2.16 kg according to the ISO1133-2011 standard.

[0018] As a preferred embodiment of the spray-free sprinkle effect polypropylene composite material of the present invention, the mass grafting rate of glycidyl methacrylate in the glycidyl methacrylate grafted POE is 0.8% to 3%. Optionally, the mass grafting rate of glycidyl methacrylate can specifically be any one of 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3% or the range value of any two of them. The test method for the mass grafting rate of glycidyl methacrylate grafted POE is FTIR, the test condition is potassium bromide tablet pressing, and the epoxy characteristic peak area is calculated for the test.

[0019] As a preferred embodiment of the spray-free sprinkle-effect polypropylene composite material of the present invention, the spray-free sprinkle-effect polypropylene composite material further comprises at least one of a light stabilizer, a lubricant, an antioxidant, and a mineral filler. Optionally, the weathering agent may specifically be 0.2 to 2 parts by weight, the lubricant may specifically be 0.2 to 2 parts by weight, the antioxidant may specifically be 0.2 to 2 parts by weight, and the mineral filler may specifically be 0 to 20 parts by weight.

[0020] Optionally, the light stabilizer is at least one of a benzotriazole light stabilizer, a benzophenone light stabilizer, a salicylate light stabilizer, a triazine light stabilizer, a substituted acrylonitrile light stabilizer, a hindered amine light stabilizer, and an organic nickel chelate; the antioxidant is a primary antioxidant and a secondary antioxidant, the primary antioxidant is a hindered phenol antioxidant and / or an aromatic amine antioxidant, and the secondary antioxidant is a phosphite antioxidant and / or a thioester antioxidant; the lubricant is at least one of an amide lubricant, a metal soap lubricant, a fatty acid lubricant, a fatty acid ester lubricant, and a fatty alcohol lubricant; the mineral filler includes at least one of talc powder, calcium carbonate, barium sulfate, and mica powder.

[0021] In a second aspect, the present invention provides a method for preparing the above spray-free sprinkle-effect polypropylene composite material, comprising the following steps: mixing the components evenly and then melt-extruding to obtain the spray-free sprinkle-effect polypropylene composite material.

[0022] Among them, a twin-screw extruder can be used for melt-extrusion in the above preparation method. The temperature of the first zone of the twin-screw extruder is 80 to 120 °C, the temperature of the second to fifth zones is 180 to 200 °C, and the temperature of other zones is 200 to 230 °C; the length-diameter ratio of the screw is (36 to 48):1.

[0023] In a third aspect, the present invention provides an application of the above spray-free sprinkle-effect polypropylene composite material in the preparation of automotive interior or exterior parts.

[0024] In a fourth aspect, the present invention provides an automotive exterior or interior part, which is mainly made of the above spray-free sprinkle-effect polypropylene composite material.

[0025] Compared with the prior art, the beneficial effects of the present invention are:

[0026] The present invention uses glycidyl methacrylate-grafted POE as a compatibilizer, which is combined with a recycled polypropylene resin containing paint residues. The epoxy groups in the compatibilizer are used to promote the uniform dispersion of the paint residues in the composite material, and by controlling the particle size distribution of the paint residues, an excellent dotting appearance effect is presented. At the same time, the compatibilizer is also used to enhance the molecular chain entanglement between the recycled polypropylene resin, polypropylene resin, and POE elastomer, so that the polypropylene composite material has good mechanical properties. Detailed Embodiments

[0027] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0028] Other materials, reagents, etc. used in the examples and comparative examples can be obtained from commercial channels without special instructions.

[0029] 1. Raw Materials and Reagents

[0030] 1) Polypropylene Resin

[0031] PP Resin 1 (homopolymer PP), with a melt mass flow rate of 24 g / 10 min (230 °C / 2.16 kg), produced by SINOPEC & SK Global Chemical Co., Ltd., and the grade is PPH-Y26 (SZ30S);

[0032] PP Resin 2 (homopolymer PP), with a melt mass flow rate of 3 g / 10 min (230 °C / 2.16 kg), produced by SINOPEC & SK Global Chemical Co., Ltd., and the grade is PP PPH-T03 (ZHONGHAN);

[0033] PP Resin 3 (block copolymer PP), with a melt mass flow rate of 28 g / 10 min (230 °C / 2.16 kg), produced by Guangzhou Petrochemical, and the grade is PP K9930 (GUANGZHOU).

[0034] 2) POE Elastomer

[0035] POE Elastomer 1 (ethylene-butene copolymer), with a melt mass flow rate of 4 g / 10 min (190 °C / 2.16 kg), produced by LG Chem, and the grade is POE LC565;

[0036] POE Elastomer 2 (ethylene-butene copolymer), with a melt mass flow rate of 1 g / 10 min (190 °C / 2.16 kg), produced by LG Chem, and the grade is POE LC168.

[0037] 3) Compatibilizer

[0038] Compatibilizer 1 (POE-g-GMA), where the mass grafting rate of GMA is 1.0%, the manufacturer is Jiayirong, and the grade is SOG-02;

[0039] Compatibilizer 2 (POE-g-GMA), where the mass grafting rate of GMA is 2.4%, the manufacturer is Jiayirong, and the grade is SOG-03.

[0040] 4) Recycled polypropylene resin

[0041] Recycled polypropylene resin 1, where the melt mass flow rate of the polypropylene resin is 30 g / 10 min, and the particle size D of the paint residue 50 is 200 μm;

[0042] Recycled polypropylene resin 2, where the melt mass flow rate of the polypropylene resin is 30 g / 10 min, and the particle size D of the paint residue 50 is 300 μm;

[0043] Recycled polypropylene resin 3, where the melt mass flow rate of the polypropylene resin is 40 g / 10 min, and the particle size D of the paint residue 50 is 100 μm;

[0044] Recycled polypropylene resin 4, where the melt mass flow rate of the polypropylene resin is 30 g / 10 min, and the particle size D of the paint residue 50 is 50 μm;

[0045] Recycled polypropylene resin 5, where the melt mass flow rate of the polypropylene resin is 30 g / 10 min, and the particle size D of the paint residue 50 is 500 μm;

[0046] The above recycled polypropylene resins 1-5 are all from the recycled granulated materials of partially de-painted automotive bumpers from Hunan Xinjiyuan; among them, the mass percentage of the paint residue in the recycled granulated materials of the automotive bumper is 0.5%, and different particle sizes of the paint residue are obtained by crushing and screening. The particle size D of the paint residue 50 can be measured by a laser particle size analyzer (Malvern Panalytical, model MAZ3000).

[0047] 5) The additives are composed of a primary antioxidant (antioxidant 1010), a secondary antioxidant (antioxidant 168), a weathering agent (light stabilizer t-81), and a lubricant (N,N'-ethylenebisstearamide) in a mass ratio of 1:1:1:1.

[0048] 2. Preparation method of the spray-free sprinkling effect polypropylene composite material of the present invention

[0049] According to the formula, after mixing each component evenly, add it to a twin-screw extruder, melt extrude and pelletize to obtain a spray-free sprinkle-effect polypropylene composite material; among them, the temperature of the first zone of the twin-screw extruder is 80-120 °C, the temperature of the second to fifth zones is 180-200 °C, and the temperature of other zones is 200-230 °C.

[0050] Table 1 Weight parts of each component of the spray-free sprinkle-effect polypropylene composite material in each example and comparative example

[0051]

[0052]

[0053] 3. Performance testing

[0054] 1) Mechanical property testing: Tensile strength is tested according to the ISO 527-2012 standard, and the tensile rate is 50 mm / min; Izod notched impact strength is tested according to the ISO 180-2019 standard, and the notch type is 1eA type notch.

[0055] 2) Evaluation of sprinkle appearance effect: Inject the spray-free sprinkle-effect polypropylene composite materials in each example and comparative example into 50 mm × 50 mm samples. Randomly select 5 samples for each example or comparative example, and then count the average value of the number of sprinkles on each sample (select particles with a diameter ≥ 30 μm, which are visible to the naked eye); the more the number of sprinkles, the better the sprinkle appearance effect.

[0056] Table 2 Spray-free sprinkle-effect polypropylene composite materials in each example and comparative example

[0057]

[0058]

[0059] According to the data in Table 2, it can be seen that the tensile strength of the polypropylene composite materials in Examples 1-11 reaches above 17 MPa, and the Izod notched impact strength reaches above 15 KJ / m 2 above, and at the same time the number of sprinkles reaches 107-245 pieces / 2500 mm 2, indicating that the polypropylene composite material of the present invention not only has good mechanical properties but also has excellent sprinkle appearance effect. At the same time, it can be seen from Example 1, Comparative Example 1 and Comparative Example 2 that when the particle size of the paint residue in the recycled polypropylene resin is too small or too large, a good sprinkle appearance effect cannot be achieved; especially when the particle size of the paint residue is too large, it will also lead to a decrease in the mechanical properties of the polypropylene composite material. In addition, it can be found from Comparative Example 3 that when the polypropylene composite material lacks the glycidyl methacrylate-grafted POE compatibilizer, it will not only lead to a decrease in its mechanical properties but also significantly reduce its sprinkle appearance effect.

[0060] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polypropylene composite material with a spray-free scattering effect, characterized in that: The composition comprises the following components by weight: 50 to 65 parts of polypropylene resin I, 10 to 20 parts of POE elastomer, 3 to 20 parts of compatibilizer, and 5 to 30 parts of polypropylene resin recycled material; The compatibilizer is glycidyl methacrylate grafted POE; The polypropylene resin recycled material includes polypropylene resin II and paint residue, and the particle size D of the paint residue is 50 It is 100~400μm.

2. The spray-free scattering effect polypropylene composite material according to claim 1, characterized in that: The invention comprises the following components by weight: 55 to 60 parts of polypropylene resin I, 12 to 18 parts of POE elastomer, 8 to 12 parts of compatibilizer and 10 to 20 parts of recycled polypropylene resin.

3. The spray-free scattering effect polypropylene composite material according to claim 1, characterized in that: The polypropylene resin I adopts ISO1133-2011 standard, and the melt mass flow rate at 230°C and 2.16kg is 8-25g / 10min; And / or, the polypropylene resin II adopts ISO1133-2011 standard, and has a melt mass flow rate of 28 to 50 g / 10 min at 230° C. and 2.16 kg.

4. The spray-free scattering effect polypropylene composite material according to claim 1, characterized in that: The polypropylene resin recycled material is derived from automobile bumper recycled material.

5. The spray-free scattering effect polypropylene composite material according to claim 1, characterized in that: The POE elastomer includes at least one of ethylene-octene copolymer, ethylene-butene copolymer and ethylene-propylene copolymer.

6. The spray-free scattering effect polypropylene composite material according to claim 1, characterized in that: The mass grafting rate of glycidyl methacrylate in the glycidyl methacrylate grafted POE is 0.8% to 3%.

7. The spray-free scattering effect polypropylene composite material according to claim 1, characterized in that: The components of the spray-free sprinkle-effect polypropylene composite material also include at least one of a weathering agent, a lubricant, an antioxidant, and a mineral filler.

8. The method for preparing the spray-free scattering effect polypropylene composite material according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: mixing the components uniformly and then melting and extruding them to obtain a polypropylene composite material with spray-free scattering effect.

9. Use of the spray-free scattering effect polypropylene composite material according to any one of claims 1 to 7 in the preparation of automotive interior or exterior parts.

10. An automobile exterior or interior trim, characterized in that: The invention is mainly made of the polypropylene composite material with spray-free sprinkling effect as described in any one of claims 1 to 7.

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