Polypropylene composite material as well as preparation method and application thereof

Abstract

The invention provides a polypropylene composite material as well as a preparation method and application thereof, and the polypropylene composite material comprises the following components in parts by weight: 50-70 parts of polypropylene resin, 3-7 parts of polyolefin elastomer, 15-20 parts of filler, 2-5 parts of hydrogen-containing silicone oil and 1-5 parts of antibacterial agent. According to the polypropylene composite material disclosed by the invention, the polyolefin elastomer, the filler, the hydrogen-containing silicone oil and the antibacterial agent are compounded with the polypropylene resin, so that the polypropylene composite material not only has high hydrophobicity and excellent antibacterial and mildew-proof properties, but also has good temperature resistance and mechanical properties and low cost, and can meet performance requirements in different fields; for example, the use requirement on the dishwasher is met.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a polypropylene composite material and a preparation method and application thereof. Background Art

[0002] Polypropylene plastic is a material with excellent comprehensive performance and relatively low cost, and is widely used in various fields of production and life. Polypropylene is a thermoplastic plastic formed by the polymerization of propylene monomers. Its molecular formula is (C3H6)n, the molecular weight is 420,000-1.6 million, the molecular structure is relatively simple, and it is mainly composed of carbon and hydrogen atoms. Polypropylene has a carbon-hydrogen bond in its molecular structure, and carbon and hydrogen have similar electronegativity, so the molecular polarity is small, and it is not easy to interact with polar substances such as water, and it has a certain hydrophobicity. However, due to its simple molecular structure, its hydrophobicity is not as obvious as other polymer materials. Therefore, in the processing of polypropylene, its hydrophobicity is usually changed by adding additives and using surface treatment to meet the needs of different fields.

[0003] For example, Chinese invention patent document CN107163389A discloses a highly hydrophobic and scratch-resistant polypropylene material and its preparation method, wherein the polypropylene material improves the hydrophobicity of the surface of the polypropylene material by adding a fluorine-containing additive and compounding nano zinc oxide. However, the proportion of the hydrophobic additive added is large, 4-23%, the cost is high, and the material does not have antibacterial and mildew-proof functions, and the temperature resistance is also lacking.

[0004] Therefore, developing a polypropylene material with high hydrophobicity, excellent antibacterial and mildew-proof properties, excellent mechanical properties and temperature resistance and low cost is an urgent problem to be solved in this field. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a polypropylene composite material and a preparation method and application thereof. The polypropylene composite material solves the problem that the polypropylene material in the prior art cannot have high hydrophobicity, excellent antibacterial and mildew resistance, good temperature resistance and mechanical properties and low cost.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a polypropylene composite material, which comprises, by weight, 50 to 70 parts of polypropylene resin, 3 to 7 parts of polyolefin elastomer, 15 to 20 parts of filler, 2 to 5 parts of hydrogen-containing silicone oil and 1 to 5 parts of antibacterial agent.

[0008] In the present invention, by adding hydrogen-containing silicone oil, a transparent film is easily formed on the surface of the polypropylene composite material, thereby giving the material very excellent hydrophobicity and oleophobicity; by adding an antibacterial agent, the material is given excellent antibacterial and mildew-proof properties, and by controlling the addition ratio of the hydrogen-containing silicone oil and the antibacterial agent, the compatibility of the system can be good, and the original physical properties of the polypropylene can be well retained; by compounding the polyolefin elastomer, filler, hydrogen-containing silicone oil and the antibacterial agent with the polypropylene resin, the polypropylene composite material not only has high hydrophobicity and excellent antibacterial and mildew-proof properties, but also has good temperature resistance and mechanical properties and low cost, and can meet the performance requirements of different fields, for example, meet the use requirements of the polypropylene composite material on the dishwasher.

[0009] In the present invention, 50 to 70 parts of the polypropylene resin may be, for example, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 66 parts, 68 parts, 70 parts, etc.

[0010] In the present invention, the mass percentage of the polypropylene resin in the polypropylene composite material is ≥50%, more preferably ≥60%, and particularly preferably 60-70%.

[0011] In the present invention, 3 to 7 parts of the polyolefin elastomer can be, for example, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts, 5.2 parts, 5.5 parts, 5.8 parts, 6 parts, 6.2 parts, 6.5 parts, 6.8 parts, 7 parts, etc.

[0012] In the present invention, 15 to 20 parts of filler can be, for example, 15 parts, 15.2 parts, 15.5 parts, 15.8 parts, 16 parts, 16.2 parts, 16.5 parts, 16.8 parts, 17 parts, 17.2 parts, 17.5 parts, 17.8 parts, 18 parts, 18.2 parts, 18.5 parts, 18.8 parts, 19 parts, 19.2 parts, 19.5 parts, 19.8 parts, 20 parts, etc.

[0013] In the present invention, 2 to 5 parts of hydrogen-containing silicone oil can be, for example, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 2.9 parts, 3 parts, 3.1 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 3.9 parts, 4 parts, 4.1 parts, 4.2 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.8 parts, 5 parts, etc.

[0014] In the present invention, the mass percentage of hydrogen silicone oil in the polypropylene composite material is 2-5%, for example, it can be 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, etc.; more preferably, it is 2-4%.

[0015] In the present invention, 1 to 5 parts of antibacterial agent can be, for example, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 2.9 parts, 3 parts, 3.1 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 3.9 parts, 4 parts, 4.1 parts, 4.2 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.8 parts, 5 parts, etc.

[0016] In the present invention, the mass percentage of the antibacterial agent in the polypropylene composite material is 2-5%, for example, it can be 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, etc.; more preferably, it is 2-3%.

[0017] Preferably, the polypropylene resin comprises homopolypropylene and / or copolymer polypropylene.

[0018] Preferably, the polypropylene resin includes homopolypropylene and copolymer polypropylene, and the mass ratio of the homopolypropylene to the copolymer polypropylene is (1-2):1, wherein the specific values ​​in (1-2) can be, for example, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, etc.

[0019] In the present invention, the polypropylene resin can be selected from at least one of PP K8009 of Sinopec and PP 3015 of Yongjiaen.

[0020] Preferably, the polyolefin elastomer comprises a linear ethylene-octene copolymer.

[0021] Preferably, at 190°C and 2.16kg, the melt index of the polyolefin elastomer is 0.5-5g / 10min, for example, 0.5g / 10min, 0.8g / 10min, 1g / 10min, 1.2g / 10min, 1.5g / 10min, 1.8g / 10min, 2g / 10min, 2.2g / 10min, 2.5g / 10min, 2.8g / 10min, 3g / 10min, 3.2g / 10min, 3.5g / 10min, 3.8g / 10min, 4g / 10min, 4.2g / 10min, 4.5g / 10min, 4.8g / 10min, 5g / 10min, etc.

[0022] In the present invention, the polyolefin elastomer may be selected from at least one of LC175 of LG Chemical and POE8150 of Dow.

[0023] Preferably, the filler comprises talc.

[0024] In the present invention, talcum powder is used as filler, which can improve the temperature resistance of the polypropylene composite material, so that the material can be used for a long time under extreme conditions of high temperature; it can also reduce the shrinkage rate of the polypropylene composite material, improve the dimensional stability of the material, and solve the problem that large parts are prone to warping and deformation; in addition, it can also reduce costs.

[0025] Preferably, the particle size D50 of the filler is 1 to 15 μm, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, etc.

[0026] In the present invention, the particle size of the filler can be known from the manufacturer's information, or can be obtained by conventional testing methods, such as testing with a laser particle size analyzer.

[0027] In the present invention, the talc powder can be selected from the ultrafine talc powder KC-6300# produced by Beihai Group.

[0028] Preferably, the hydrogen-containing silicone oil includes hydrogen-containing methyl silicone oil.

[0029] Preferably, the mass content of hydrogen in the hydrogen-containing silicone oil is 0.75-1.6%, for example, it can be 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1%, 1.05%, 1.1%, 1.15%, 1.2%, 1.25%, 1.3%, 1.35%, 1.4%, 1.45%, 1.5%, 1.55%, 1.6%, etc.; more preferably, it is 1.2-1.6%.

[0030] In the present invention, the hydrogen-containing silicone oil is hydrogen-modified methyl silicone oil, that is, a part of the methyl groups in the methyl silicone oil are replaced by hydrogen groups; the mass content of the hydrogen-containing silicone oil is within the above range, which can effectively improve the coverage and retention rate of the transparent film, and further improve the hydrophobic and oleophobic properties of the polypropylene composite material.

[0031] Preferably, the antibacterial agent comprises a silver-zinc composite antibacterial agent.

[0032] Preferably, the mass ratio of silver to zinc in the silver-zinc composite antibacterial agent is (6-12):1, wherein the specific values ​​in (6-12) can be, for example, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, etc.

[0033] In the present invention, a silver-zinc composite antibacterial agent is used. Compared with silver-based antibacterial agents or zinc-based antibacterial agents, the antibacterial property of the polypropylene composite material is improved, meeting the requirements of materials such as dishwashers for antibacterial and mildew-proof properties.

[0034] Preferably, the polypropylene composite material further comprises, by weight, at least one of 1 to 3 parts of a compatibilizer (for example, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, etc.), 0.3 to 0.5 parts of an antioxidant (for example, 0.3 parts, 0.32 parts, 0.34 parts, 0.36 parts, 0.38 parts, 0.4 parts, 0.42 parts, 0.44 parts, 0.46 parts, 0.48 parts, 0.5 parts, etc.), or 0.5 to 1 parts of a lubricant (for example, 0.5 parts, 0.52 parts, 0.55 parts, 0.58 parts, 0.6 parts, 0.65 parts, 0.7 parts, 0.75 parts, 0.8 parts, 0.85 parts, 0.9 parts, 0.95 parts, 1 part, etc.).

[0035] Preferably, the compatibilizer comprises maleic anhydride grafted polypropylene.

[0036] Preferably, the grafting rate of the maleic anhydride grafted polypropylene is 0.5-1%, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% and the like.

[0037] Preferably, the antioxidant comprises a hindered phenol antioxidant and / or a phosphite antioxidant.

[0038] In the present invention, the antioxidant is preferably a composite antioxidant composed of a hindered phenol antioxidant and a phosphite antioxidant; the hindered phenol antioxidant exemplarily includes but is not limited to pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010); the phosphite antioxidant exemplarily includes but is not limited to (2,4-di-tert-butylphenyl) triester phosphite (antioxidant 168).

[0039] Preferably, the lubricant comprises a fatty amide lubricant and / or pentaerythritol stearate.

[0040] In the present invention, the fatty amide lubricant includes ethylene bisstearamide.

[0041] In a second aspect, the present invention provides a method for preparing the polypropylene composite material according to the first aspect, the preparation method comprising the following steps:

[0042] The polypropylene resin, polyolefin elastomer, filler, hydrogen-containing silicone oil and antibacterial agent are mixed and extruded to obtain the polypropylene composite material.

[0043] Preferably, the mixing speed is 350-500 rpm, for example, 350 rpm, 400 rpm, 450 rpm, 500 rpm, etc.; the mixing time is 4-6 min, for example, 4 min, 4.5 min, 5 min, 5.5 min, 6 min, etc.

[0044] Preferably, the extrusion temperature is 190-210°C, for example, 190°C, 195°C, 200°C, 205°C, 210°C, etc.; the rotation speed is 350-420rpm, for example, 350rpm, 360rpm, 380rpm, 400rpm, 420rpm, etc.

[0045] In a third aspect, the present invention provides a highly hydrophobic antibacterial and mildew-proof product, wherein the highly hydrophobic antibacterial and mildew-proof product comprises the polypropylene composite material described in the first aspect;

[0046] Preferably, the highly hydrophobic antibacterial and mildew-proof product comprises a dishwasher.

[0047] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] In the present invention, the polypropylene composite material is compounded with polyolefin elastomer, filler, hydrogen-containing silicone oil and antibacterial agent with polypropylene resin in specific contents, so that the polypropylene composite material not only has high hydrophobicity and excellent antibacterial and mildew-proof properties, but also has good temperature resistance and mechanical properties and low cost, and can meet the performance requirements of different fields. DETAILED DESCRIPTION

[0050] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0051] The materials used in the present invention can be obtained from commercial sources or prepared by conventional methods. Unless otherwise specified, the materials used in the present invention are as follows:

[0052] Polypropylene resin (PP)

[0053] PP-1: Homopolymer polypropylene, PP HP500N from CNOOC and Shell.

[0054] PP-2: Copolymer polypropylene, PP K8009 from Sinopec.

[0055] Polyolefin elastomer (POE): LC175 from LG Chem.

[0056] Filler: talcum powder, Beihai Group's ultra-fine talcum powder KC-6300#.

[0057] Hydrogenated silicone oil (H)

[0058] H1: Hydrogen content is 1.6% by mass, Japan Shin-Etsu KF-99.

[0059] H2: Hydrogen content is 1.2% by mass, JC1120.

[0060] H3: Hydrogen content is 0.75% by mass, JC 1075.

[0061] Antimicrobial agents

[0062] 1: Silver-zinc composite antibacterial agent, NAFUR RHA-TZ inorganic antibacterial and antifungal agent, the mass ratio of silver to zinc is 9:1.

[0063] 2: Silver-based antibacterial agent, Nippon Koa Nitro Corporation, Meiling Kangle PG721ST.

[0064] Compatibilizer: Maleic anhydride grafted polypropylene, Bochen PC-1B

[0065] Antioxidant: a compound of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0066] Lubricant: Ethylene bisstearamide.

[0067] Examples 1 to 6

[0068] Examples 1 to 6 respectively provide a polypropylene composite material, and the formula of the polypropylene composite material is shown in Table 1 in parts by weight; wherein, “ / ” indicates that the component is not included in the formula.

[0069] The preparation method of the polypropylene composite material comprises: adding each component into a high-speed mixer, adjusting the mixer speed to 450 rpm, stirring for 4 minutes, and then transferring to a twin-screw extruder, extruding, cooling, granulating, and drying to obtain the polypropylene composite material; wherein the process parameters of the twin-screw extruder are: processing temperature of 200° C., and screw speed of 380 rpm.

[0070] Table 1

[0071]

[0072] Performance Testing

[0073] The polypropylene composite materials provided in Examples 1 to 6 were dried and then injection molded to obtain standard test specimens. The injection molding process conditions were as follows: nozzle temperature was 210°C, the temperatures of each zone were 180°C, 190°C, and 210°C, the holding time was 10s, and the injection pressure was 50MPa. The obtained test specimens were subjected to the following performance tests:

[0074] (1) Tensile strength: Tested in accordance with international standard ISO 527.

[0075] (2) Flexural strength: Tested in accordance with international standard ISO 178.

[0076] (3) Flexural modulus: tested in accordance with international standard ISO 178.

[0077] (4) Notched impact strength: tested in accordance with international standard ISO 180.

[0078] (5) Antibacterial performance: Tested in accordance with international standard ISO 22196.

[0079] (6) Hydrophobicity: Tested according to ASTM D7444-07.

[0080] The specific test results are shown in Table 2.

[0081] Table 2

[0082]

[0083]

[0084] As can be seen from Table 2, the polypropylene composite material provided by the present invention, by adding hydrogen-containing silicone oil and antibacterial agent and compounding with polyolefin elastomer, filler and polypropylene resin, not only makes the polypropylene composite material have high hydrophobicity and excellent antibacterial and mildew-proof properties, but also has good temperature resistance and mechanical properties and low cost, and can meet the performance requirements of different fields, such as meeting its use requirements on dishwashers; the polypropylene composite material has a tensile strength of ≥24.6MPa, a flexural strength of ≥39.5MPa, a flexural modulus of ≥1980MPa, an antibacterial rate of Escherichia coli of ≥90.2%, an antibacterial rate of Staphylococcus aureus of ≥88.0%, and a water contact angle of ≥110°.

[0085] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A polypropylene composite material, characterized in that: In parts by weight, the polypropylene composite material comprises 50 to 70 parts of polypropylene resin, 3 to 7 parts of polyolefin elastomer, 15 to 20 parts of filler, 2 to 5 parts of hydrogen-containing silicone oil and 1 to 5 parts of antibacterial agent.

2. The polypropylene composite material according to claim 1, characterized in that: The polypropylene resin includes homopolypropylene and / or copolymer polypropylene; Preferably, the polypropylene resin includes homopolypropylene and copolymer polypropylene, and the mass ratio of the homopolypropylene to the copolymer polypropylene is (1-2):

1.

3. The polypropylene composite material according to claim 1 or 2, characterized in that: The polyolefin elastomer comprises a linear ethylene-octene copolymer; Preferably, at 190° C. and 2.16 kg, the melt index of the polyolefin elastomer is 0.5 to 5 g / 10 min.

4. The polypropylene composite material according to any one of claims 1 to 3, characterized in that: The filler includes talc; Preferably, the particle size D50 of the filler is 1 to 15 μm.

5. The polypropylene composite material according to any one of claims 1 to 4, characterized in that: The hydrogen-containing silicone oil includes hydrogen-containing methyl silicone oil; Preferably, the mass content of hydrogen in the hydrogen-containing silicone oil is 0.75-1.6%, more preferably 1.2-1.6%.

6. The polypropylene composite material according to any one of claims 1 to 5, characterized in that: The antibacterial agent includes a silver-zinc composite antibacterial agent; Preferably, the mass ratio of silver to zinc in the silver-zinc composite antibacterial agent is (6-12):

1.

7. The polypropylene composite material according to any one of claims 1 to 6, characterized in that: The polypropylene composite material further comprises at least one of 1 to 3 parts of a compatibilizer, 0.3 to 0.5 parts of an antioxidant, or 0.5 to 1 parts of a lubricant, in parts by weight; Preferably, the compatibilizer comprises maleic anhydride grafted polypropylene; Preferably, the grafting rate of maleic anhydride grafted polypropylene is 0.5-1%; Preferably, the antioxidant comprises a hindered phenol antioxidant and / or a phosphite antioxidant; Preferably, the lubricant comprises a fatty amide lubricant and / or pentaerythritol stearate.

8. A method for preparing a polypropylene composite material according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: The polypropylene resin, polyolefin elastomer, filler, hydrogen-containing silicone oil and antibacterial agent are mixed and extruded to obtain the polypropylene composite material.

9. The preparation method according to claim 8, characterized in that: The mixed material further includes at least one of a compatibilizer, an antioxidant or a lubricant; Preferably, the mixing speed is 350-500 rpm and the mixing time is 4-6 min; Preferably, the extrusion temperature is 190-210° C., and the rotation speed is 350-420 rpm.

10. A highly hydrophobic, antibacterial and mildew-proof product, characterized in that: The highly hydrophobic, antibacterial and mildew-proof product comprises the polypropylene composite material according to any one of claims 1 to 7; Preferably, the highly hydrophobic antibacterial and mildew-proof product comprises a dishwasher.

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