A scratch-resistant and anti-sticky polypropylene material and its preparation method and application

Abstract

The present invention discloses a scratch-resistant and anti-sticking polypropylene material, its preparation method, and application, relating to the technical field of polymer materials. The scratch-resistant and anti-sticking polypropylene material comprises: a polypropylene matrix, a silicate, white oil, and an organic anti-scratch agent. The polypropylene matrix comprises a first polypropylene and a second polypropylene in a mass ratio of 1:(10-20), and the difference in melt index between the first and second polypropylenes is ≥20 g / 10 min. The present invention uses the first and second polypropylenes with a melt index difference of ≥20 g / 10 min as the polypropylene matrix to form a two-phase polypropylene matrix with different crystallinity. The addition of white oil and silicate can induce interfacial transcrystallization at the interface of the two-phase polypropylene matrix, thereby enhancing the migration barrier effect of the organic anti-scratch agent and reducing surface stickiness caused by the decomposition of the organic anti-scratch agent after migration to the material surface.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and more particularly to a scratch-resistant and anti-sticking polypropylene material, a preparation method thereof, and applications thereof. Background Art

[0002] Polypropylene is widely used in automobiles due to its low density, high cost-effectiveness, excellent heat resistance, rigidity, chemical resistance, ease of processing, molding, and recycling, making it the most widely used and fastest-growing automotive plastic. The rapid development of the automotive industry in recent years has placed increasingly stringent requirements on interior and exterior materials. For example, instrument panels, door panels, and bumpers require high strength, impact resistance, scratch resistance, and good dimensional stability.

[0003] However, since the surface of polypropylene is easily scratched by external forces, it will greatly affect the appearance of the product and limit its wide application in automotive interior products. Currently, most of the scratch resistance of polypropylene materials is improved by adding scratch resistant agents. Organic scratch resistant agents such as amide scratch resistant agents have good compatibility with polypropylene and good scratch resistance modification effects, but they are easy to migrate to the surface of polypropylene and decompose, causing the surface of polypropylene to become sticky, affecting the use effect.

[0004] Patent CN106188845A proposes a lightweight automobile pillar guard plate, which adds a scratch-resistant additive to a polypropylene and branched polypropylene system to improve the scratch resistance. The scratch-resistant additive is selected from silicone, polytetrafluoroethylene, polyether siloxane, and calcium silicate. The tensile strength can reach 38.6-65.3 MPa, but the scratch resistance and anti-stickiness properties are poor and need further improvement. Summary of the Invention

[0005] The purpose of the present invention is to overcome the defects and shortcomings of existing polypropylene materials, such as poor scratch resistance and easy surface stickiness, and to provide a scratch-resistant and anti-sticking polypropylene material.

[0006] Another object of the present invention is to provide a method for preparing a scratch-resistant and anti-sticking polypropylene material.

[0007] Another object of the present invention is to provide a use of the above-mentioned scratch-resistant and anti-sticking polypropylene material in the preparation of automotive interior or exterior products.

[0008] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0009] The present invention provides a scratch-resistant and anti-sticking polypropylene material comprising the following components in parts by weight:

[0010]

[0011]

[0012] The polypropylene matrix comprises a first polypropylene and a second polypropylene in a mass ratio of 1:(10-20), and a difference in melt index between the first polypropylene and the second polypropylene at 230° C. and 2.16 kg is ≥20 g / 10 min.

[0013] The scratch-resistant and anti-sticking polypropylene material of the present invention utilizes a first polypropylene and a second polypropylene with a melt index difference of ≥20 g / 10 min as the polypropylene matrix. Leveraging their different crystallization properties, the two-phase polypropylene matrix is ​​formed with different crystallinity. The addition of white oil and silicate synergistically induces interfacial transcrystallization at the interface of the two-phase polypropylene matrix, thereby enhancing the migration barrier of the organic scratch-resistant agent, allowing the organic scratch-resistant agent to slowly migrate to the polypropylene surface, thereby reducing surface stickiness caused by the decomposition of the organic scratch-resistant agent after migration. Furthermore, the white oil improves the compatibility of the silicate in the polypropylene matrix, facilitating its migration to the surface. The silicate reacts with moisture and / or carbon dioxide in the air to form a dense protective film on the polypropylene surface, improving scratch resistance while further preventing the decomposition and stickiness of the organic scratch-resistant agent.

[0014] In some embodiments, the polypropylene matrix accounts for no less than 75 wt% of the polypropylene material; preferably 75-85 wt%, more preferably 78-82 wt%.

[0015] In some embodiments, the difference in melt index between the first polypropylene and the second polypropylene at 230° C. and 2.16 kg is denoted as Δn, and 20≤Δn≤100 g / 10 min.

[0016] In some embodiments, the melt index difference Δn that can achieve the purpose of the present invention can be selected from 20g / 10min, 21g / 10min, 22g / 10min, 23g / 10min, 24g / 10min, 25g / 10min, 26g / 10min, 27g / 10min, 28g / 10min, 29g / 10min, 30g / 10min, 31g / 10min, 32g / 10min, 33g / 10min, 34g / 10min, 35g / 10min, 36g / 10min, 37g / 10min , 38g / 10min, 39g / 10min, 40g / 10min, 41g / 10min, 42g / 10min, 43g / 10min, 44g / 10min, 45g / 10min, 46g / 10min, 47g / 10min, 48g / 10min, 49g / 10min, 50g / 10min, 51g / 10min, 52g / 10min, 53g / 10min, 54g / 10min, 55g / 10min, 56g / 10min, 57g / 10min, 58g / 10min, 59g / 10min, 60g / 10min, 61g / 10min, 62g / 10min, 63g / 10min, 64g / 10min, 65g / 10min, 66g / 10min, 67g / 10min, 68g / 10min, 69g / 1 0min, 70g / 10min, 71g / 10min, 72g / 10min, 73g / 10min, 74g / 10min, 75g / 10min, 76g / 10min, 77g / 10min, 78g / 10min, 79g / 10min, 80g / 10min, 81g / 10min, 82g / 10min, 83g / 10min, 84g / 10min, 85g / 10min, 86g / 10min, 87g / 10min, 88g / 10min, 89g / 10min, 90g / 1 0min, 91g / 10min, 92g / 10min, 93g / 10min, 94g / 10min, 95g / 10min, 96g / 10min, 97g / 10min, 98g / 10min, 99g / 10min and 100g / 10min.

[0017] The first polypropylene and the second polypropylene of the present invention are polypropylenes (PP) with different melt indexes. As long as the difference in melt index between the two is ≥20g / 10min, there is no special requirement for the type and melt index range of the first polypropylene or the second polypropylene.

[0018] In some embodiments, the polypropylene matrix is ​​one or more of homopolymer polypropylene, random copolymer polypropylene or block copolymer polypropylene.

[0019] In some embodiments, the first or second polypropylene has a melt index of 0.5 to 100 g / 10 min at 230°C and 2.16 kg. The melt index is also known as the melt flow rate (MFR). When the melt flow rate is within this range, the polypropylene material system has good fluidity, which facilitates uniform mixing of the raw material components and produces a polypropylene material with excellent performance. The melt flow rate (MFR) is measured according to the ISO 1133-1:2011 standard method.

[0020] In some embodiments, the melt index of the first polypropylene or the second polypropylene at 230°C and 2.16 kg can be selected from 0.5g / 10min,1g / 10min,2g / 10min,3g / 10min,4g / 10min,5g / 10min,6g / 10min,7g / 10min,8g / 10min,9g / 10min,10g / 10min,11g / 10min,12g / 10min,13g / 10min,14g / 10min,15g / 10min,16g / 10min,17g / 10min,18g / 10min,19g / 10min,20g / 10min,21g / 10min,22g / 10min,23g / 10min,24g / 10min,25g / 10min,26g / 10min,27g / 10min,28g / 10min,29g / 10min,30g / 10min,31g / 10min,32g / 10min,33g / 10min,34g / 10min,35g / 10min,36g / 10min,37g / 10min,38g / 10min,39g / 10min,40g / 10min,41g / 10min,42g / 10min,43g / 10min,44g / 10min,45g / 10min,46g / 10min,47g / 10min,48g / 10min,49g / 10min,50g / 10min,51g / 10min,52g / 10min,53g / 10min,54g / 10min,55g / 10min,56g / 10min,57g / 10min,58g / 10min,59g / 10min,60g / 10min,61g / 10min,62g / 10min,63g / 10min,64g / 10min,65g / 10min,66g / 10min,67g / 10min,68g / 10min,69g / 10min,70g / 10min,71g / 10min,72g / 10min,73g / 10min,74g / 10min,75g / 10min,76g / 10min,77g / 10min,78g / 10min,79g / 10min,80g / 10min,81g / 10min,82g / 10min,83g / 10min,84g / 10min,85g / 10min,86g / 10min,87g / 10min,88g / 10min,89g / 10min,90g / 10min,91g / 10min,92g / 10min,93g / 10min,94g / 10min,95g / 10min,96g / 10min,97g / 10min,98g / 10min,99g / 10min,99.5g / 10min and 100g / 10min.

[0021] In some embodiments, the first polypropylene has a melt index of 50-100 g / 10 min at 230° C. and 2.16 kg.

[0022] In some embodiments, the second polypropylene has a melt index of 0.5-35 g / 10 min at 230° C. and 2.16 kg.

[0023] When the melt index of the first polypropylene and the second polypropylene is within the above range, the comprehensive performance of Rockwell hardness (HCR) and scratch resistance is better.

[0024] In some embodiments, the silicate is one or more of aluminosilicate, sodium silicate, magnesium silicate or olivine.

[0025] The white oil mentioned in the present invention refers to paraffin oil or liquid paraffin, which is mainly obtained from crude oil fractionation.

[0026] In some embodiments, the kinematic viscosity of the white oil at 40°C is 30-100 mm 2 / S.

[0027] In some embodiments, the organic anti-scratch agent is a silicone anti-scratch agent and / or an amide anti-scratch agent. The addition of silicone anti-scratch agents and amide anti-scratch agents can effectively improve the scratch resistance of polypropylene materials, while having good compatibility with polypropylene and not easily damaging the mechanical properties of polypropylene materials.

[0028] In some embodiments, the organic anti-scratch agent is one or more of silicone powder, oleamide or erucamide.

[0029] In some embodiments, 0.1-10 parts of functional additives are also included; the functional additives include but are not limited to flame retardants, antioxidants, and antistatic agents; conventional flame retardants, antioxidants, and antistatic agents in the art can be used in the present invention.

[0030] The present invention protects a method for preparing a scratch-resistant and anti-sticking polypropylene material, comprising the following steps: uniformly mixing a polypropylene matrix, a silicate, white oil and an organic scratch-resistant agent, and then melt-blending and extruding the mixture to obtain the scratch-resistant and anti-sticking polypropylene material.

[0031] In some embodiments, the temperatures of each zone of the twin-screw extruder are 170°C-180°C, 200°C-210°C, 200°C-210°C, 210°C-220°C, 210°C-220°C, 205°C-210°C, 205°C-210°C, 205°C-210°C, 200°C-210°C, and 200°C-210°C from the feeding section to the die head.

[0032] The present invention protects the use of a scratch-resistant and anti-sticking polypropylene material in the preparation of automobile interior or exterior decoration products.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] The present invention provides a scratch-resistant and anti-sticking polypropylene material. The material utilizes a first polypropylene and a second polypropylene with a melt index difference of ≥20 g / 10 min as a polypropylene matrix. Leveraging their different crystallization properties, the material forms a two-phase polypropylene matrix with different crystallinity. The addition of white oil and a silicate can induce interfacial transcrystallization at the interface of the two-phase polypropylene matrix, thereby enhancing the migration barrier of an organic scratch-resistant agent, allowing the agent to slowly migrate to the polypropylene surface, thereby reducing surface stickiness caused by the decomposition of the organic scratch-resistant agent upon migration. Furthermore, the white oil improves the compatibility of the silicate in the polypropylene matrix, facilitating its migration to the surface. The silicate reacts with moisture and / or carbon dioxide in the air to form a dense protective film on the polypropylene surface, enhancing scratch resistance while further preventing the decomposition and stickiness of the organic scratch-resistant agent.

[0035] The scratch-resistant and anti-sticking polypropylene material of the present invention has a Rockwell hardness of 80 or more, a 0-day scratch resistance ΔL of 0.6 or less, and a 180-day scratch resistance ΔL of 1 or less. DETAILED DESCRIPTION

[0036] The present invention will be further described below in conjunction with specific embodiments, but the examples do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the examples of the present invention are conventionally purchased raw materials and reagents.

[0037] The raw materials in the following examples and comparative examples are as follows:

[0038] 1. Polypropylene:

[0039] PP-1: copolymer polypropylene resin, EP5075X, purchased from Sinopec; melt mass flow rate 50 g / 10 min at 230°C and 2.16 kg;

[0040] PP-2: homopolymer polypropylene resin, H9018, purchased from Sinopec; melt mass flow rate 50 g / 10 min at 230°C and 2.16 kg;

[0041] PP-3: copolymerized polypropylene resin, BX3900, purchased from SK Company of South Korea; melt index 60g / 10min;

[0042] PP-4: copolymer polypropylene resin, EPN31MA, purchased from Iran Petrochemical Company; 230°C, 2.16 kg melt mass flow rate of 100 g / 10 min;

[0043] PP-5: homopolymer polypropylene resin, B1101, purchased from Sinopec; melt flow rate at 230°C and 2.16 kg: 0.5 g / 10 min;

[0044] PP-6: Homopolymer polypropylene: K1008, purchased from Yanshan Petrochemical Company; 230°C, 2.16 kg melt mass flow rate of 10 g / 10 min;

[0045] PP-7: copolymerized polypropylene resin: EP300M, purchased from Sinopec; melt mass flow rate of 10 g / 10 min at 230°C and 2.16 kg;

[0046] PP-8: block copolymer polypropylene, K9010, purchased from Taiwan Chemical Company; 230°C, 2.16 kg melt mass flow rate of 10 g / 10 min;

[0047] PP-9: homopolymer polypropylene resin, Z30S, purchased from Dalian Petrochemical Co., Ltd.; melt mass flow rate of 20 g / 10 min at 230°C and 2.16 kg;

[0048] PP-10: homopolymer polypropylene resin: N-Z30S, purchased from Maoming Petrochemical Company; at 230°C, 2.16 kg melt mass flow rate of 28 g / 10 min;

[0049] PP-11: copolymer polypropylene, 7751, purchased from Li Changrong Chemical Company; at 230°C, the melt mass flow rate of 2.16 kg was 32 g / 10 min.

[0050] 2. White oil:

[0051] White oil 1, kinematic viscosity at 40°C is 90 mm 2 / S, purchased from Idemitsu Co., Ltd., Japan;

[0052] White oil 2, kinematic viscosity at 40°C is 40 mm 2 / S, purchased from CNOOC.

[0053] 3. Silicate:

[0054] Potassium aluminosilicate, commercially available;

[0055] Magnesium silicate, commercially available.

[0056] 4. Scratch resistant agent:

[0057] Silicone powder, commercially available;

[0058] Oleamide, commercially available.

[0059] 5. Functional additives:

[0060] Antioxidant, 1010, commercially available.

[0061] The present invention provides a method for preparing a scratch-resistant and anti-sticking polypropylene material, comprising the steps of uniformly mixing a polypropylene matrix, a silicate, white oil, an organic anti-scratch agent, and a functional additive, melt-blending and extruding the mixture in an extruder, and granulating the mixture to obtain the scratch-resistant and anti-sticking polypropylene material. The temperatures of the zones of the twin-screw extruder are, from the feed section to the die, 175°C, 205°C, 205°C, 215°C, 215°C, 208°C, 208°C, 205°C, and 205°C, respectively.

[0062] The test methods and standards for the scratch-resistant and anti-sticking polypropylene materials of the embodiments and comparative examples of the present invention are as follows:

[0063] (1) Shore hardness test: The test standard is GB / T3398.2-2008.

[0064] (2) Scratch resistance test: The grid scratch test method is to draw a grid on the material surface with a fixed load and spacing, and then record and evaluate the color change of the scratches. The scratch resistance of the material surface is characterized by the whitening degree of the scratches. The grid is drawn using an Irisin cross-notch tester with a load of 10N. The L value (reflecting the depth of the color) before and after scratching is tested using a colorimeter, and ΔL is calculated. The larger the ΔL value, the more obvious the whitening of the color after scratching, and the worse the scratch resistance of the material.

[0065] Examples 1 to 18

[0066] This embodiment provides a series of scratch-resistant and anti-sticking polypropylene materials, the components by mass are shown in Table 1.

[0067] Table 1

[0068]

[0069] Table 2

[0070]

[0071]

[0072] Comparative Examples 1-11

[0073] This embodiment provides a series of scratch-resistant and anti-sticking polypropylene materials, the components by mass are shown in Table 3-4.

[0074] Table 3

[0075]

[0076] Table 4

[0077]

[0078] Performance Testing

[0079] The scratch-resistant and anti-sticking polypropylene materials of the examples and comparative examples were subjected to performance tests. The test results are shown in Table 5 below.

[0080] Table 5 Performance test results

[0081]

[0082]

[0083] As can be seen from Table 5, the scratch-resistant and anti-sticking polypropylene material of the present invention has a Rockwell hardness of 80 or more, a 0-day scratch resistance ΔL of 0.6 or less, and a 180-day scratch resistance ΔL of 1 or less.

[0084] The results of Examples 1-3 show that when the polypropylene matrix contains copolymerized polypropylene and / or block polypropylene, the dispersion of the raw materials in the matrix is ​​better, the overall performance of the obtained polypropylene material is better, and during use, the scratch-resistant agent is not easily migrated to the surface of the material and becomes sticky. Therefore, the scratch-resistant retention performance of the material is also better.

[0085] The results of Examples 4-6 show that as the melt index difference increases, the scratch resistance of the polypropylene material shows a trend of first increasing and then decreasing. Within a suitable range, the melt index difference is within a suitable range, which can further improve the comprehensive performance of the polypropylene material.

[0086] The results of Example 7 and Example 1, and Example 8 and Example 5 show that when the melt index of the first polypropylene with a higher melt index is selected within the range of 50-100 g / 10 min, and the melt index of the second polypropylene with a lower melt index is selected within the range of 0.5-35 g / 10 min, the resulting polypropylene material has better scratch resistance retention performance.

[0087] The results in Examples 9-11 show that the hardness of the polypropylene material can be further improved by using the ratio of the two melt index polypropylenes within an appropriate range.

[0088] The results of Example 9 and Examples 12-14 show that white oils and silicates commonly used in the art can be used in the present invention and have little effect on the properties of the polypropylene material.

[0089] The results of Example 9 and Examples 15-18 show that when the amount of each raw material is within the above range of the present invention, the hardness and scratch resistance of the obtained polypropylene material are good.

[0090] In the polypropylene matrices of Comparative Examples 1-3, when the difference in melt index between the two polypropylenes is less than 20 g / 10 min, the scratch resistance retention performance of the prepared polypropylene material is significantly reduced.

[0091] In Comparative Examples 4-6, the polypropylene resin selected had no difference in melt index, or a single polypropylene was selected, and the hardness and scratch resistance of the prepared polypropylene material were significantly deteriorated.

[0092] In Comparative Example 7, the amount of white oil used was too much, and the resulting polypropylene material had insufficient crystallinity, resulting in a significant decrease in hardness. At the same time, during use, small molecules easily migrated, and the surface became sticky, resulting in a significant decrease in scratch resistance after 180 days. In Comparative Example 10, the magnesium silicate content was too high, and inorganic particles easily agglomerated in the polypropylene matrix, affecting the crystallization properties of the polypropylene and resulting in a decrease in hardness.

[0093] Comparative Example 8 did not add white oil, and Comparative Example 9 did not add magnesium silicate, and the scratch resistance of the obtained polypropylene deteriorated significantly. Comparative Example 11 did not add a scratch resistance agent, and the scratch resistance of the polypropylene deteriorated significantly.

[0094] The above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications may be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention are intended to be included within the scope of protection of the claims of the present invention.

Claims

1. A scratch-resistant and anti-sticky polypropylene material, characterized in that: The composition comprises the following components in parts by weight: The polypropylene matrix comprises a first polypropylene and a second polypropylene in a mass ratio of 1:(10-20), and the difference in melt index between the first polypropylene and the second polypropylene at 230° C. and 2.16 kg is 22-50 g / 10 min.

2. The scratch-resistant and anti-sticking polypropylene material according to claim 1, characterized in that: The melt index of the first polypropylene and the second polypropylene at 230° C. and 2.16 kg is 0.5 to 100 g / 10 min.

3. The scratch-resistant and anti-sticking polypropylene material according to claim 1 or 2, characterized in that: The melt index of the first polypropylene at 230° C. and 2.16 kg is 50-100 g / 10 min.

4. The scratch-resistant and anti-sticking polypropylene material according to claim 1 or 2, characterized in that: The melt index of the second polypropylene at 230° C. and 2.16 kg is 0.5-35 g / 10 min.

5. The scratch-resistant and anti-sticking polypropylene material according to claim 1, characterized in that: The first polypropylene and the second polypropylene are one or more of homopolymer polypropylene, random copolymer polypropylene or block copolymer polypropylene.

6. The scratch-resistant and anti-sticking polypropylene material according to claim 1, characterized in that: The silicate is one or more of aluminosilicate, sodium silicate, magnesium silicate or olivine.

7. The scratch-resistant and anti-sticking polypropylene material according to claim 1, characterized in that: The kinematic viscosity of the white oil at 40°C is 30-100 mm 2 / S.

8. The scratch-resistant and anti-sticking polypropylene material according to claim 1, characterized in that: The organic anti-scratch agent is a silicone anti-scratch agent and / or an amide anti-scratch agent.

9. A method for preparing the scratch-resistant and anti-sticking polypropylene material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: uniformly mixing a polypropylene matrix, silicate, white oil and an organic scratch-resistant agent, and performing melt blending and extrusion to obtain the scratch-resistant and anti-sticking polypropylene material.

10. Use of the scratch-resistant and anti-sticking polypropylene material according to any one of claims 1 to 8 in the preparation of automotive interior or exterior products.

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