Patent Application
20200216651
The present invention relates to polypropylene compositions, and more particularly to a lightweight polypropylene composition that has a specific weight below 1.05, and is suitable for large components such as doors, windows, automotive parts and housings of home appliances due to its high toughness and high rigidity.
Plastic forms a range of the most popular non-metallic materials, and is extensively used in various applications, including doors, windows, automotive parts and components as well as diverse containers.
Among plastic materials, polyolefin resins are desirable for having low specific weights, low prices, and good toughness. However, the development of new polyolefin composites is often subject to the difficulty in reaching good balance among different physical properties. Particularly, when used as materials for producing large components such as automotive bumpers and housings of home appliances through injection molding, polyolefin composites need to be lightweight and properly mobile.
The physical quantities to be considered for evaluation of plastic materials include impact strength (toughness) and flexural modulus (rigidity), which are two conflicting properties. That is, a highly rigid plastic material is not the one having excellent toughness. On the contrary, a highly tough plastic material cannot have excellent rigidity. Therefore, during formation of composites, rubber or inorganic materials may be added as a solution for modification.
To give a polypropylene composite with a high rigidity modulus, inorganic materials may be introduced in an enhanced amount. For example, polyethylene and styrene-butadiene rubber may be introduced with an inorganic filler such as calcium carbonate to achieve improved toughness in the resulting polypropylene composite. Alternatively, elastomer, ultra-high molecular weight polyethylene, or low-density linear polyethylene may be used to for toughening modification of the resulting polypropylene composite. However, this can increase the specific weight of the resulting polypropylene composite, and is against the trend toward lightweightness.
In addition, toughening modification for polypropylene composites as performed in the prior art out no extra attention to the overall mobility of the resulting polypropylene composites. While an addition of the elastomer greater than 10% of the total weight of the polypropylene composite does effectively improve the polypropylene composite in terms of toughness and in turn impact strength, the high viscosity of the elastic rubber unavoidably makes the resulting composition less mobile.
The primary objective of the present invention is to provide a lightweight, high-toughness, high-rigidity polypropylene composition, which is made with a compatibilizer introduced that is made by grafting polypropylene on maleic anhydride. The compatibilizer not only improves interfacial bonding between inorganic powder and the polypropylene composition, but also endows the polypropylene composition with excellent resistance to impact (high toughness), good flexural modulus (high rigidity) and proper mobility for processing. With the ingredients introduced in a properly arranged order, the resulting polypropylene composition that has good balance among lightweightness, toughness and rigidity, thereby satisfying the need unmet in the prior art for a polypropylene composition that is lightweight and tough, yet rigid enough.
Also provided by the present invention is a manufacturing method of the foregoing polypropylene composition. The method includes first preparing a masterbatch by grafting inorganic powder and a coupling agent on a polypropylene resin, and extruding the masterbatch so that the coupling agent is cross-linked to the surface of the inorganic powder to enhance affinity among macromolecules; and melting and extruding the masterbatch together with the polypropylene resin and other additives, so as to obtain the polypropylene composition that has good balance among lightweightness, toughness and rigidity
More particularly, the inorganic powder used in the present invention has been mixed with a polypropylene resin and a coupling agent into masterbatch in advance, so that the inorganic powder disperses well in the polypropylene composition.
Another objective of the present invention is to provide a lightweight, high-toughness, high-rigidity polypropylene composition, having a specific weight ranging between 1.0 and 1.05, and being characterized in having a flexural modulus at 23° C. of 1832-2038 MPa as measured according to standards as set forth in ISO178 and 179, and simply supported beam notch impact strength of 40.2-55.8 kJ/m2, and being composed of the following components in amounts based on and jointly amount to 100 wt % of a total weight of the polypropylene composition:
The manufacturing method of polypropylene compositions of the present invention comprises the following steps:
According to the present invention, a novel polypropylene composition is made by mixing and coextruding a polypropylene resin with additives. Therein, the polypropylene resin is a propylene-ethylene copolymer, which has a content of comonomer ethylene ranging between 1 and 10 wt %. Its mobility is expressed as a melt flow index (or MI) tested with parameters of 230° C. and 2.16 kg. The selection of MI is made with the consideration to molding processability and mechanical properties of the final product. The greater the molecular weight a polypropylene resin has, the smaller the MI and the poorer the mobility it has, making it unsuitable for injection molding. A polypropylene resin with an excessively great MI has poor toughness and is brittler. A proper MI range of the polypropylene resin is 0.5-100 g/10 min. In the present invention, the polypropylene resin used comprises 75-96 wt % of a propylene-ethylene copolymer having an MI of 30-60 g/10 min and 4-25 wt % of a propylene-ethylene copolymer having an MI of 1-20 g/10 min.
The inorganic powder in the polypropylene composition of the present invention is selected from spherical or irregular talcum, mica, and calcium carbonate.
Alternatively, it may be inorganic compound whisker, such as one or more of silicon carbide, magnesium oxide, silicon oxide, magnesium sulfate and calcium sulfate. The inorganic powder has received surface treatment or surface finish to have improved processability and physical properties. The inorganic powder has an average grain diameter ranging between 0.01 and 20 μm. Therein, the fine-particle-size inorganic powder is added in an amount of 10-20 wt %, and any adding amount greater than 20 wt % can make the composition to sticky to easily process. High length-diameter ratio inorganic powder is added in an amount of 3-6 wt %, and any adding amount greater than 6 wt % can make the final product have rough surface.
The fine-particle-size inorganic powder is talcum powder. Therein, the talcum powder has an average grain diameter of 0.1-3l m and is selected from fine-mesh talcum powder. It is used to improve the polypropylene composition in terms of rigidity. Generally, the talcum powder is added in the composition with an amount higher than 10 wt % because any adding amount below this threshold can turn out to be ineffective in improving rigidity. Nevertheless, with too much talcum powder added, the filler has poor dispersion, adversely affect the molding processability and physical properties of the final product, and any adding amount greater than 20-wt % can undesirably increase the final product in specific weight. According to the present invention, the fine-particle-size inorganic powder is added in an amount of 10-20 wt %.
In the present invention, the high length-diameter ratio inorganic powder used is magnesium sulfate whisker, which is a single-crystal fiber. It has a length-diameter ratio of 10-60 or higher, but it has the optimal physical properties when the length-diameter ratio is 30-50. Whisker is close to perfect crystal, and has excellent mechanical properties such as high strength and high modulus, making them act as backbones in the polypropylene composition and be able to endow the composite with great strength. Whisker preferably has a small diameter because an increased diameter risks the whisker of more internal defects. Whisker with fewer defects has greater strength. For this reason, the whisker for strengthening purposes preferably has a high length-diameter ratio.
The inorganic powder used in the present invention has received surface treatment. To this end, the surface treatment agent used may be zinc stearate, titanate, silanes or other coupling agents. For the purpose of surface modification, the surface treatment agent is added in the amount equal to 3-4 wt % of the inorganic powder. The inorganic powder may be talcum, mica, or calcium carbonate. Alternatively, it may be whisker of an inorganic compound, such as silicon carbide, magnesium oxide, silicon oxide, magnesium sulfate, and calcium sulfate. With proper surface treatment or surface finish, it can have improved dispersion in organic resins, thereby enhancing processability and mechanical properties of the final product.
As used in the present invention, the masterbatch is made by mixing and co-extruding inorganic powder that has received surface treatment with a polypropylene resin using a twin-screw extruder. Therein, the inorganic powder is one or a combination of talcum powder and whisker. The fine-particle-size talcum powder is added in an amount of 10-20 wt %, and the whisker is added in an amount of 3-6 wt %. The polypropylene resin is a propylene-ethylene copolymer having a melt flow index (MI) of 30-60 g/10 min. and is added in an amount of 70-85 wt %.
In the present invention, the toughener used is rubber or a thermoplastic elastomer, for improving the polypropylene composition in terms of toughness. Therein, the rubber may be one or more selected from ethylene-propylene-diene monomer (EPDM), styrene-butadiene rubber (SBR), nitrile butadiene rubber (NBR) and ethylene-propylene rubber (EPR).
The thermoplastic elastomer may be one or more selected from ethylene-octene copolymer (POE), styrene-butadiene-styrene (SBS) and hydrogenated SBS (SEBS).
The toughener is well compatible to the polypropylene resin, so that the polypropylene composition so prepared has good balance between toughness and rigidity, allowing the polypropylene composition to show optimal properties.
The compatibilizer used in the present invention is a compatibilizer made by grafting polypropylene on maleic anhydride (PP-g-MA). To prepare the same, maleic anhydride (MA), polypropylene resin (PP) and dicumylperoxide (DCP) are weighted and mixed at high speed, before extruded by a twin screw extruder at 180 to 200° C. and granulated. The PP-g-MA has both a polar end (MA) and a non-polar end (PP), making it a good compatibilizer when MA is bound with the inorganic powder (polar) and PP has physical entanglement with polypropylene long chains (nonpolar) in the composition, so as to improve interfacial bonding between the inorganic powder and macromolecules.
In the present invention, the anti-oxidant used is one or a combination of a thermal antioxidant or an optical antioxidant. The thermal antioxidant may be CHINOX 1010, 1330 or B168 or a mixture with other anti-oxidants, and the optical antioxidant may be Chimassorb 2020, Tinuvin 770 or 783 or a mixture with other anti-oxidants.
The polypropylene composition of the present invention is made by mixing and co-extruding the polypropylene resin, the inorganic powder, the toughener, the coupling agent, the compatibilizer and the anti-oxidant using a twin screw extruder at 180-220° C. and 200-250 rpm, and cooling and granulating the extrudent. Therein, the inorganic powder may be in the form of a masterbatch premixed with the polypropylene resin, so as to be well distributed in the polypropylene composition, thereby significantly improving the composition in terms of toughness, rigidity and mobility.
The polypropylene composition of the present invention has excellent resistance to impact and to bonding, as well as has good mobility. Some examples and comparative examples described below are to explain the present invention but not intended to limit the scope of the present invention.
1. Preparation of the Compatibilizer (PP-g-MA):
To prepare the compatibilizer for the present invention, 5 parts by weight of maleic anhydride (MA), 100 parts by weight of polypropylene resin (PP), and 0.5 parts by weight of dicumyl peroxide (DCP) were mixed at high speed and extruded using a twin-screw extruder into grains at a temperature ranging between 180 and 200° C.
2, The polypropylene compositions made in Examples and Comparative Examples were tested for their physical properties using the following protocols, and the results are show in in Table 1:
As shown in Table 1, Example 1 involves details described as follows:
The materials and the manufacturing method as mentioned in the description related to Example 1 were used, with the compositional proportions of the materials changed to 72.2 parts of high-melting-index polypropylene, 10 parts of low-melting-index polypropylene, 10 parts of fine-particle-size talcum powder, 6 parts of magnesium sulfate whisker, 0.5 parts of silane coupling agent, 1 parts of toughener, 0.2 parts of compatibilizer, 0.1 parts by weight of anti-oxidant, as shown in Table 1.
The materials and the manufacturing method as mentioned in the description related to Example 1 were used, with the compositional proportions of talcum powder and whisker changed to 13 parts and 3 parts, respectively, while the other components and corporations were identical to Example 2, as shown in Table 1.
The materials and the manufacturing method as mentioned in the description related to Example 1 were used, with the compositional proportions of the materials changed to 56.9 parts of high-melting-index polypropylene, 16 parts of low-melting-index polypropylene, 17 parts of talcum powder, 4 parts of magnesium sulfate whisker, 0.9 parts of silane coupling agent, 5 parts of toughener, 0.1 parts of compatibilizer, 0.1 parts of anti-oxidant, as shown in Table 1.
The materials and the manufacturing method as mentioned in the description related to Example 1 were used, with the compositional proportions of the materials changed to 56.6 parts of high-melting-index polypropylene, 16 parts of low-melting-index polypropylene, 17 parts of talcum powder, 4 parts of magnesium sulfate whisker, 0.9 parts of silane coupling agent, 5 parts of toughener, 0.4 parts of compatibilizer, 0.1 parts of anti-oxidant, as shown in Table 1.
The materials and the manufacturing method as mentioned in the description related to Example 1 were used, with the compositional proportions of the materials changed to 60.9 parts of high-melting-index polypropylene, 16 parts of low-melting-index polypropylene, 21 parts of talcum powder, 2 parts of ethylene-octene copolymer elastomer, 0.1 parts of anti-oxidant, as shown in Table 1. None of the magnesium sulfate whisker, the silane coupling agent and the compatibilizer PP-g-MA was added.
The materials and the manufacturing method as mentioned in the description related to Example 1 were used, with the compositional proportions of the materials changed to 65.9 parts of high-melting-index polypropylene, 13 parts of low-melting-index polypropylene, 17 parts of large-grain-diameter talcum powder (having an average grain diameter of 3-6 μm, and a loss on ignition of 8%), 4 parts of magnesium sulfate whisker, 0.1 parts of anti-oxidant, as shown in Table 1. None of the silane coupling agent, the ethylene-octene copolymer elastomer toughener and compatibilizer PP-g-MA was added.
The materials and the manufacturing method as mentioned in the description related to Comparative Example 2 were used, with the compositional proportions of the materials changed to 66.9 parts of high-melting-index polypropylene, 13 parts of low-melting-index polypropylene, 10 parts of large-grain-diameter talcum powder, 10 parts of magnesium sulfate whisker, 0.1 parts of anti-oxidant, as shown in Table 1.
