A styrene alloy material and a preparation method and application thereof

Abstract

The application discloses a styrene alloy material and a preparation method and application thereof, and the styrene alloy material comprises the following components in parts by weight: 40-80 parts of polystyrene resin, 5-20 parts of polypropylene resin, 2-8 parts of a compatilizer, 5-17 parts of a toughening agent, 3-10 parts of inorganic fillers, 1-5 parts of a surface modifier, and 0.2-1 part of an auxiliary agent; the surface modifier is organic silicon. The styrene alloy material has the characteristics of high rigidity and low surface free energy, and can be applied to the fields of medical materials, low surface energy materials, cosmetic packaging and water treatment.

Description

Technical Field

[0001] The present invention relates to the technical field of general plastics, and in particular to a styrene alloy material, a preparation method and an application thereof. Background Art

[0002] High-impact polystyrene (HIPS) resin is a high-impact polystyrene product produced by adding 2%-15% styrene-butadiene or butadiene rubber particles to polystyrene (PS) resin. Compared to PS resin, HIPS resin offers higher toughness while retaining the ease of molding and processing characteristic of PS resin. It can be molded using methods such as injection molding, extrusion, and vacuum forming. It is widely used in applications such as household appliances, equipment, electronic products, furniture, household appliances, telecommunications, electronics, computers, disposable products, pharmaceuticals, and packaging. HIPS resin offers comparable shrinkage and dimensional stability to ABS resin, and its relatively low price suggests it is poised to gradually replace ABS in many industries and fields. However, compared to ABS resin, the rigidity of common HIPS resin is significantly lower. Existing research has shown that by preparing alloys and toughening them with toughening agents, impact strength comparable to ABS resin can be achieved. However, the rigidity, especially tensile strength, of these alloys is significantly lower than that of ABS resin. This lack of rigidity, particularly in rapid prototyping applications, can lead to product deformation, limiting its application.

[0003] In addition, studies have found that compared with ABS resin, styrene-acrylonitrile copolymer (SAN), polymethyl methacrylate (PMMA) and polycarbonate (PC) resin, HIPS resin has higher surface free energy and its surface can be easily wetted by aqueous solution, thus limiting its application in medical materials, low surface energy materials, cosmetic packaging and water treatment.

[0004] Therefore, how to overcome the performance deficiencies of polystyrene resin materials such as low rigidity and relatively high surface free energy and provide a polystyrene material with high rigidity and low surface free energy is an urgent problem to be solved. Summary of the Invention

[0005] To overcome the above-mentioned shortcomings of the prior art, the present invention provides a styrene alloy material, its preparation method, and its application. The present invention greatly improves the rigidity and hydrophobicity of the styrene alloy material, and has important significance in the medical, packaging, and water treatment industries.

[0006] This is achieved specifically through the following technical solutions:

[0007] A styrene alloy material, comprising the following components in parts by weight:

[0008]

[0009] Furthermore, the polystyrene resin is selected from general-purpose polystyrene, high-impact polystyrene or a mixture of the two, and the melt flow rate of the polystyrene resin is 4-10 g / 10 min under the test temperature of 200° C. and the load of 5 kg, and the test standard is GB / T 3682-2000.

[0010] Furthermore, the polypropylene resin is a copolymerized polypropylene, and its melt flow rate (MFR) is 5-10 g / 10 min at a test temperature of 230°C and a load of 2.16 kg, as tested in accordance with GB / T 3682-2000. Because PP resin has a greater shrinkage than PS, selecting a polypropylene within this MFR range results in an alloy material with superior mechanical properties and lower surface energy, i.e., a smaller contact angle, at the same PP content. In other words, while maintaining the same contact angle, selecting a PP resin within this MFR range allows the PP resin content to be appropriately reduced, thereby reducing the alloy material's shrinkage and improving its dimensional stability.

[0011] Furthermore, the compatibilizer is styrene grafted polypropylene, wherein the styrene grafting rate is preferably 5-10%. Within this grafting rate range, the alloy material has better mechanical properties, such as impact strength and tensile strength. At the same time, due to the better dispersion of polypropylene in the styrene resin matrix, it has lower surface free energy, that is, a lower contact angle.

[0012] Furthermore, the toughening agent is a polyolefin elastomer, and the polyolefin elastomer is preferably a linear triblock copolymer of styrene-butadiene rubber, polystyrene and ethylene-butene (SEBS), wherein styrene-butadiene rubber is a copolymer of styrene and butadiene.

[0013] Furthermore, the inorganic filler is mineral powder, and the mineral powder is one or more of calcium carbonate, talc and wollastonite.

[0014] Furthermore, the surface modifier is a hydrophobic silicone, preferably silicone oil and / or silicone. This can be pure silicone or a silicone masterbatch with a silica or resin carrier. The effective silicone content in the silicone masterbatch is 40-50 wt%. Silicone has a low surface energy and can effectively improve the hydrophobicity of the material. The degree of improvement is directly determined by the uniform dispersion of the silicone on the material surface. By adding PP and a suitable compatibilizer to PS resin, the uniformity of the silicone on the resin surface can be effectively improved, significantly enhancing the hydrophobicity.

[0015] Furthermore, the auxiliary agent is an antioxidant and / or a lubricant.

[0016] The antioxidant is one of a phenolic compound and a phosphite compound or a mixture of the two; the lubricant can be ethylene bis fatty acid amide (EBS) and its metal soap compound, or can be a stearic acid compound such as zinc stearate and calcium stearate.

[0017] The present invention also provides a method for preparing the above-mentioned styrene alloy material, comprising the following steps:

[0018] S1: Weigh and pre-mix the components according to the ratio to obtain a premix;

[0019] S2: The premix of step S1 is put into an extruder for melt blending and extrusion granulation to obtain the styrene alloy material.

[0020] Furthermore, the extruder is a twin-screw extruder, the aspect ratio of the twin-screw extruder is (40-44):1, the temperature of the twin-screw extruder from the feed port to the die head is 170-200°C, the pressure is 2-3MPa, and the screw speed of the twin-screw extruder is 200-400r / min.

[0021] The present invention also provides applications of the styrene alloy material in pharmaceutical materials, low surface energy materials, cosmetic packaging and water treatment.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The present invention improves the hydrophobicity of the material by adding a suitable surface modifier. PP is added to the polystyrene resin. Adding part of PP can improve the hydrophobicity and synergistically reduce the surface free energy with the surface modifier. DETAILED DESCRIPTION

[0024] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0025] <Preparation of Examples and Comparative Examples>

[0026] The raw materials used in the examples and comparative examples of the present invention are all commercially available, but are not limited to these materials:

[0027] Polystyrene resin 1: general-purpose polystyrene, melt flow rate of 8 g / 10 min, brand GPPS 123P, purchased from Shanghai Secco;

[0028] Polystyrene resin 2: high impact polystyrene, melt flow rate of 4 g / 10 min, brand HIPS MA5210, purchased from Jiangsu Yashide;

[0029] Copolymer polypropylene 1: melt flow rate of 9 g / 10 min, brand PP EP300M, purchased from CNOOC Shell;

[0030] Copolymer polypropylene 2: melt flow rate of 5 g / 10 min, brand M500R, purchased from Shanghai Petrochemical;

[0031] Copolymer polypropylene 3: melt flow rate of 2.5 g / 10 min, brand K8003, purchased from Shanghai Petrochemical;

[0032] Copolymer polypropylene 4: melt flow rate of 15 g / 10 min, brand YPJ-1215C, purchased from Yangzi Petrochemical;

[0033] Compatibilizer 1: Grafting rate 5.1%, homemade in the laboratory;

[0034] Compatibilizer 2: Grafting rate 9.6%, homemade in the laboratory;

[0035] Compatibilizer 3: Grafting rate 3.3%, homemade in the laboratory;

[0036] Compatibilizer 4: Grafting rate is 10.5%, homemade in the laboratory;

[0037] The homemade method of the compatibilizer is as follows: the production device is a twin-screw extruder, a certain amount of peroxide initiator, styrene monomer and PP resin are mixed evenly, and then added to the twin-screw extruder for extrusion and granulation. The temperature of the twin-screw extruder from the feeding port to the die head is 180-210°C, the speed of the twin-screw extruder is 200-400rpm, the pressure is 2-3MPa, and the vacuum degree is lower than 0.1MPa; the aspect ratio of the twin-screw extruder is 48:1-56:1.

[0038] Unless otherwise specified, the grafting rate in the present invention is quantitatively tested by comparing the absorbance ratio of characteristic absorption peaks in the infrared spectrum of the grafted product.

[0039] Inorganic filler: talc powder, brand TYY-777A, purchased from Haicheng Tianyuan Chemical;

[0040] Toughener 1: brand SEBS 6151, purchased from Taiwan Rubber Co., Ltd., Taiwan, China;

[0041] Toughener 2: brand SBS YH-792E, purchased from Yueyang Petrochemical;

[0042] Surface modifier 1: silicone powder, brand RM4-7081, purchased from Dow Corning, USA;

[0043] Surface modifier 2: dimethyl silicone oil, brand PMX-200, purchased from Dow Corning, USA;

[0044] Surface modifier 3: fumed silica, brand AEROSI L R202, purchased from Degussa;

[0045] Primary antioxidant: phenolic antioxidant, commercially available, the same commercial product was used in parallel experiments;

[0046] Secondary antioxidant: phosphite antioxidant, commercially available, the same commercial product was used in parallel experiments.

[0047] The preparation methods of the embodiments of the present invention and the comparative examples are as follows:

[0048] S1: According to the ratios in Table 1 and Table 3, weigh and pre-mix the components to obtain a premix;

[0049] S2: The premix of step S1 is put into a twin-screw extruder for melt blending and extrusion granulation to obtain a styrene alloy material.

[0050] The screw length-diameter ratio of the twin-screw extruder is 40:1, the temperature of the twin-screw extruder from the feed port to the die head is 170-200°C, the pressure is 2-3MPa, and the screw speed of the twin-screw extruder is 350r / min.

[0051] The term "part(s)" in this specification means "part(s) by weight" unless otherwise specified.

[0052] <Test Standard>

[0053] The performance test standards of the embodiments and comparative examples of the present invention are as follows:

[0054] Tensile strength: GB / T1040.1-2018, Test method for tensile properties of plastics;

[0055] Flexural modulus: GB / T9341-2008, Test method for flexural properties of plastics;

[0056] Contact angle test method: ASTM D5725-1999, "Standard Test Method for Determining the Wettability and Absorbency of Covering Materials Using an Automatic Contact Angle Tester."

[0057] Table 1. Formulations of Examples 1-13

[0058]

[0059]

[0060] Table 2. Performance test results of Examples 1-13

[0061]

[0062] Table 3. Comparative Examples 1-5 Formula

[0063]

[0064]

[0065] Table 4. Performance test results of comparative examples 1-5

[0066] Test items Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Tensile strength (MPa) 35 25 33 24.2 21.8 Flexural modulus (MPa) 2450 2230 2440 2210 2030 Water contact angle (°) 83 89 85 83 84

[0067] As can be seen from the data in the examples, the styrene alloy material provided by the present invention has higher strength than the conventional HIPS material (Comparative Example 4), and can basically reach the level of ABS. At the same time, by adding a suitable PP resin and a surface modifier to the polystyrene resin, the obtained alloy material exhibits better hydrophobicity (water contact angle > 90°) and has a lower cost, and can be used in industries such as pharmaceutical materials, low surface energy materials, cosmetic packaging, and water treatment.

[0068] Compared with Example 1, Comparative Example 1 did not add a surface modifier, resulting in a decrease in the hydrophobicity of Comparative Example 1.

[0069] Compared with Example 1, in Comparative Example 2, no polypropylene resin is added to the resin matrix. The hydrophobicity of Comparative Example 2 is lower than that of Comparative Example 1, and the tensile strength and flexural modulus of Comparative Example 2 are also lower.

[0070] Compared with Example 1, in Comparative Example 3, the surface modifier is fumed silica, which has a poor effect on improving the hydrophobicity of the material.

[0071] Comparing Comparative Example 4 with Example 1, the formula of Comparative Example 4 contains only HIPS, and the tensile strength, flexural modulus and hydrophobicity of the material are not good.

[0072] Comparative Example 5 is compared with Comparative Example 1. In the formula of Comparative Example 5, only HIPS, toughening agent and talc are combined. The tensile strength, flexural modulus and hydrophobicity of the material are also very poor.

[0073] The above description is only a preferred 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 scope of protection of the present invention.

Claims

1. A polystyrene alloy material, characterized in that: Calculated by weight, it includes the following components: 40-80 parts of polystyrene resin; 5-20 parts of polypropylene resin; 2-8 parts of compatibilizer; 5-17 parts of toughening agent; 3-10 parts of inorganic filler; 1-5 parts of surface modifier; 0.2-1 part of additive; The surface modifier is silicone; the silicone is silicone oil and / or silicone; The polypropylene resin is copolymerized polypropylene, and the melt flow rate of the polypropylene resin is 5-10 g / 10 min under the test conditions of a temperature of 230° C. and a load of 2.16 kg; The compatibilizer is styrene grafted polypropylene, wherein the grafting rate of styrene is 5-10%.

2. The polystyrene alloy material according to claim 1, characterized in that: The polystyrene resin has a melt flow rate of 4-10 g / 10 min under the conditions of a test temperature of 200° C. and a load of 5 kg.

3. The polystyrene alloy material according to claim 1, characterized in that: The toughening agent is a polyolefin elastomer.

4. The polystyrene alloy material according to claim 3, characterized in that: The polyolefin elastomer is SEBS.

5. The polystyrene alloy material according to claim 1, characterized in that: The inorganic filler is mineral powder, and the mineral powder is one or more of calcium carbonate, talc and wollastonite.

6. The polystyrene alloy material according to claim 1, characterized in that: The auxiliary agent is an antioxidant and / or a lubricant.

7. A method for preparing a polystyrene alloy material according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1: Weigh and pre-mix the components according to the ratio to obtain a premix; S2: putting the premix of step S1 into an extruder, performing melt blending and extrusion granulation to obtain the polystyrene alloy material.

8. Use of the polystyrene alloy material according to any one of claims 1 to 6 in pharmaceutical materials, low surface energy materials, cosmetic packaging and water treatment.

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