Talc-reinforced pc / abs alloy material and method for producing the same

Abstract

The application discloses a talcum powder reinforced PC / ABS alloy material and a preparation method thereof. The raw materials of the composition mainly comprise polycarbonate resin (PC), acrylonitrile-styrene-diene copolymer (ABS), talcum powder and phosphoric anhydride compounds. The phosphoric anhydride compounds are prepared by the reaction of diphenyl phosphine oxide and itaconic anhydride. The obtained talcum powder reinforced PC / ABS alloy material has excellent appearance and high impact, high modulus and high heat resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer composite materials, and particularly relates to a talcum powder reinforced PC / ABS alloy material and a preparation method thereof. BACKGROUND

[0002] In recent years, thinning and lightening have become the development trend of the automobile industry, and PC / ABS alloy, as the most widely used alloy material in this field, has been required to be more and more diversified by downstream customers. For example, the high linear expansion coefficient (CLTE) of PC / ABS will cause the mismatch of parts with other material parts during installation, and the tolerance gap will be large or small during the alternating process of winter and summer, so the PC / ABS with low CLTE is developed. Thinning requires PC / ABS to have higher rigidity to resist the bending deformation of thin-walled parts.

[0003] The introduction of mineral fillers into PC / ABS alloy can increase rigidity and reduce CLTE, thereby meeting the above-mentioned thinning and lightening requirements. Glass fiber is a common filler, but its direct application in PC / ABS alloy can easily lead to fiber floating, affecting the appearance, and the fiber floating is also not conducive to post-processing such as paint spraying and water transfer printing. Talcum powder is another common filler, which has the advantages of high rigidity and low CLTE of the material, but the introduction of talcum powder will cause the toughness of PC / ABS alloy to decrease significantly and defects such as material flowers and silver wires to appear in the injection molding appearance, because on the one hand, talcum powder degrades the matrix, and on the other hand, talcum powder is difficult to disperse well in the matrix. Therefore, on the basis of ensuring the high rigidity of PC / ABS filled with talcum powder, how to reduce the toughness loss caused by the introduction of talcum powder is a very meaningful topic.

[0004] In the prior art, CN 116814056A discloses a mineral reinforced PC / ABS alloy with good appearance and high performance and a preparation method thereof, but this method needs to prepare ABS masterbatch first, which increases the production cost and production time.

[0005] Therefore, it is necessary to develop a simple method for preparing a talcum powder reinforced PC / ABS alloy material with good appearance and high performance. SUMMARY

[0006] To solve the above problems, the application provides a talcum powder reinforced PC / ABS alloy material and a preparation method thereof. The preparation process of the talcum powder reinforced PC / ABS alloy material of the application is simple and easy to implement, the alloy material prepared has excellent appearance, and has high impact, high modulus and high heat resistance.

[0007] To achieve the above application purposes, the technical scheme of the application is as follows:

[0008] The present application provides a talc reinforced PC / ABS alloy material, which is prepared from raw materials comprising the following mass fractions:

[0009] 30-70 parts, preferably 40-60 parts, of polycarbonate resin (PC);

[0010] 10-50 parts, preferably 20-40 parts, of acrylonitrile-styrene-butadiene copolymer (ABS);

[0011] 5.0-25 parts, preferably 10-20 parts, of talc;

[0012] 0.1-4 parts, preferably 0.5-2 parts, of phosphinic acid compound;

[0013] 0-5 parts, preferably 0.5-3.0 parts, of processing aid;

[0014] Specifically, the polycarbonate resin can be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, etc.; the acrylonitrile-styrene-butadiene copolymer can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc.; the talc can be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, etc.; the phosphinic acid compound can be 0.1 parts, 0.5 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, etc.; and the processing aid can be 0 parts, 0.1 parts, 0.5 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.

[0015] In one embodiment, the phosphinic acid compound is prepared by reacting diphenyl phosphine oxide with itaconic anhydride in a solvent.

[0016] Specifically, the phosphinic acid compound is prepared by the following method, comprising the steps of:

[0017] Mixing diphenyl phosphine oxide, itaconic anhydride and organic solvent, stirring to generate precipitated product, filtering and drying to obtain the phosphinic acid compound.

[0018] Preferably, the molar ratio of diphenyl phosphine oxide to itaconic anhydride is 1:1-1.5, such as 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc.

[0019] Preferably, the organic solvent is selected from one or more of ethyl acetate, methyl acetate, butyl acetate, phenyl acetate, dichloromethane, diethyl ether, preferably one or more of ethyl acetate, methyl acetate;

[0020] More preferably, the amount of the organic solvent is 1-8 times the mass of the diphenylphosphine oxide.

[0021] Preferably, the reaction, without particular requirements for the temperature, is stirred at room temperature, and the reaction time is 20-45 min, preferably 30-40 min.

[0022] Specifically, the reaction completion also includes post-processing operations such as filtration, drying, etc., which are all conventional operations in the field and are not particularly required here, for example, drying in a vacuum drying oven at 100℃ for 4h.

[0023] In an embodiment, the polycarbonate resin is selected from one or more of aromatic polycarbonates, aliphatic polycarbonates, preferably bisphenol A type polycarbonate;

[0024] Preferably, the melt flow index of the polycarbonate resin is 3-65 g / 10 min, preferably 5-50 g / 10 min, and more preferably 7-35 g / 10 min, under test conditions of 300℃ and 1.2 kg.

[0025] Preferably, the polycarbonate resin is Wanhua 2100, Wanhua 2150.

[0026] In an embodiment, the acrylonitrile-styrene-butadiene copolymer has a mass content of butadiene of 10-30%, a mass content of acrylonitrile of 15-35%, and a mass content of styrene of 50-70%.

[0027] Preferably, the acrylonitrile-styrene-butadiene copolymer is Zeon PA-757, Zeon PA-747.

[0028] In an embodiment, the talc has a particle size of 1-9μm.

[0029] Preferably, the talc is Erisys R7, Erisys 3CA.

[0030] In an embodiment, the processing aid is selected from one or more combinations of antioxidants, lubricants, toughening agents, ultraviolet absorbers, compatibilizers, light stabilizers, thermal stabilizers, metal deactivators, plasticizers, anti-adhesion agents, colorants, coupling agents, nucleating agents, foaming agents, antibacterial agents, mildewproofing agents, acid scavengers, hydrolysis-resistant agents, chain extenders, flow modifiers, matting agents, antistatic agents, reinforcing agents, fillers, anti-fogging agents, light diffusers, infrared absorbers, optical brighteners, and laser marking agents, preferably one or more of antioxidants, lubricants, and toughening agents; preferably, based on 0-5 parts of the processing aid, the respective amounts are: 0-0.5 parts of antioxidants, 0-1 parts of lubricants, and 0-4 parts of toughening agents.

[0031] Preferably, the antioxidant is selected from one or more of hindered phenols, phosphites, thioesters, benzofurans, acryloyl-modified phenols, hydroxylamine antioxidants, more preferably one or more of BASF antioxidants Irganox 1076, Irganox 1010, Irganox 168, Irgafos 126, Irgafos P-EPQ, Irganox B900;

[0032] Preferably, the lubricant is selected from one or more of fatty alcohols, fatty acids, fatty acid esters, montan waxes, amide waxes, saturated hydrocarbons, silicones and polysiloxanes, preferably pentaerythritol stearate;

[0033] Preferably, the toughening agent is selected from one or more of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic polymer, acrylic-silicone rubber-based toughening agent, ethylene-methyl acrylate, ethylene-butyl acrylate, ethylene-acrylate-glycidyl methacrylate terpolymer, preferably one or more of methyl methacrylate-butadiene-styrene copolymer, more preferably one or more of EM500, M711.

[0034] It is a common technical means in the art to add certain additives to PC materials, and the skilled person can selectively use the above-mentioned additives according to the performance characteristics of the product, and the present application does not have special requirements for the specific types and amounts of additives, which can be adjusted according to the needs based on the existing technology.

[0035] The present application also provides a preparation method of the above-mentioned talcum powder reinforced PC / ABS alloy material, which is prepared by adding each raw material into a twin-screw extruder for melt extrusion and granulation, which is a conventional method in the art and is not particularly limited.

[0036] For example, an exemplary preparation method has the following steps:

[0037] The polycarbonate resin, acrylonitrile-styrene-butadiene copolymer, phosphoric anhydride compound and processing aid are mixed according to the formula proportion, put into the main feeding port of the twin-screw extruder, at the same time, the talcum powder is put into the side feeding port, then melt extrusion and granulation to obtain the talcum powder reinforced PC / ABS alloy material.

[0038] Preferably, the temperature of the conveying section of the twin-screw extruder is set to 210-220℃, the temperature of the plasticizing section is set to 225-270℃, and the temperature of the metering section is set to 225-260℃; the screw rotation speed is 200-600rpm.

[0039] The talcum powder reinforced PC / ABS alloy material described in the present application can be widely used in the fields of automobiles, electronic appliances and the like, and is particularly suitable for applications such as automobile spoilers and integrated front faces.

[0040] The present application has the following advantages:

[0041] The present application introduces phosphoric anhydride compounds into the talc reinforced PC / ABS alloy material, which can neutralize the alkalinity of talc and protect PC resin from degradation. At the same time, the phosphoric anhydride compounds have a part of anhydride functional groups, which can react with the terminal hydroxyl groups of PC, greatly improving the compatibility of inorganic filler talc and PC, and helping talc to disperse better in the resin. The talc reinforced PC / ABS alloy material of the present application has good mechanical properties, excellent appearance performance, and the phosphoric anhydride compounds have the effect of reducing the internal stress of the material, which is beneficial to subsequent processing processes such as paint spraying and water transfer printing. DETAILED DESCRIPTION

[0042] In order to facilitate the understanding of the present application, the present application will be further described below in conjunction with examples. It should be understood that the following examples are only for better understanding of the present application, and do not mean that the present application is limited to the following examples.

[0043] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Unless otherwise specified, the reagents, materials and instruments used in the following examples are conventional reagents, conventional materials and conventional instruments in the art, which can be obtained by commercial purchase.

[0044] The main raw material source information is as follows:

[0045] Polycarbonate resin (PC): bisphenol A type polycarbonate produced by interfacial phosgene method, Clarnate 2150, melt flow index is 15 g / 10 min (300℃, 1.2 kg); Clarnate 2100, melt flow index is 10 g / 10 min (300℃, 1.2 kg); Wanhua Chemical Group Co., Ltd.;

[0046] ABS resin: ABS particles produced by blending method, PA-757, melt flow index is 19 g / 10 min (220℃, 10 kg); PA-747, melt flow index is 12 g / 10 min (220℃, 10 kg); Chi Mei Corporation;

[0047] Talc: R7, D50 is 2 μm; 3CA, D50 is 6 μm; Yire Stone Co., Ltd.;

[0048] Antioxidant: Irganox B900, BASF Corporation;

[0049] Lubricant: GLYCOLUBE PETS, pentaerythritol stearate, Longrich USA Corporation;

[0050] Toughening agent: EM500, produced by LG company in Korea; M711, produced by Zhongyuan company in Japan;

[0051] Diphenyl phosphine oxide: produced by National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0052] Itaconic anhydride: produced by National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0053] 1-Propyl phosphonic anhydride: produced by National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0054] Preparation Example 1-3:

[0055] Phosphonic anhydride compound 1: 50 g (0.247 mol) of diphenyl phosphine oxide, 28 g (0.250 mol) of itaconic anhydride were added to 300 g of ethyl acetate, stirred at room temperature for 30 min to obtain a precipitate, the insoluble substance was separated by filtration, and placed in a vacuum drying oven at 100℃ for 4 h to obtain phosphonic anhydride compound 1.

[0056] Phosphonic anhydride compound 2: 50 g (0.247 mol) of diphenyl phosphine oxide, 35 g (0.312 mol) of itaconic anhydride were added to 350 g of ethyl acetate, stirred at room temperature for 30 min to obtain a precipitate, the insoluble substance was separated by filtration, and placed in a vacuum drying oven at 100℃ for 4 h to obtain phosphonic anhydride compound 2.

[0057] Phosphonic anhydride compound 3: 50 g (0.247 mol) of diphenyl phosphine oxide, 40 g (0.357 mol) of itaconic anhydride were added to 400 g of ethyl acetate, stirred at room temperature for 30 min to obtain a precipitate, the insoluble substance was separated by filtration, and placed in a vacuum drying oven at 100℃ for 4 h to obtain phosphonic anhydride compound 3.

[0058] Example 1-4

[0059] The polycarbonate resin (PC), acrylonitrile-styrene-butadiene copolymer (ABS), phosphonic anhydride compound, antioxidant, lubricant, and toughening agent were mixed according to the raw material type and mass (unit / kg) in Table 1, and were fed into the main feeding port of the twin-screw extruder, and the talc was fed into the side feeding port, and then was melt-extruded, wherein the conveying segment temperature of the twin-screw extruder was set to 210℃, the plasticizing segment temperature was set to 240℃, the metering segment temperature was set to 230℃, and the screw rotation speed was 400 rpm, and then was pelletized to obtain a talc reinforced PC / ABS alloy material.

[0060] Comparative Example 1-4

[0061] Comparative Examples 1-4 were prepared in substantially the same manner as Example 1, except that the types and ratios of the raw materials were adjusted according to Table 1 (unit: Kg), and other parameters and operating conditions were not changed.

[0062] Table 1 Formulation of Comparative Examples 1-4 and Examples 1-4

[0063]

[0064] The properties of the talc reinforced PC / ABS alloy materials in Examples 1-4 and Comparative Examples 1-4 were tested according to the following methods, and the results are shown in Table 2:

[0065] Main Test Methods

[0066] The notched impact strength was tested according to ISO 179 standard, and the sample size was 80*10*4 mm, and the notch depth was 2.0 mm.

[0067] The heat distortion temperature (HDT) was tested according to ISO 75 standard, and the load was 1.80 MPa, and the heating rate was 120 °C / h.

[0068] The tensile strength was tested according to ISO 527, and the sample size was 170*10*4 mm, and the rate was 50 mm / min.

[0069] The tensile modulus was tested according to ISO 527, and the sample size was 170*10*4 mm, and the rate was 1 mm / min.

[0070] The appearance evaluation was performed by injection molding a large high gloss plate, and the appearance fabric pattern, silver wire and other defects were evaluated. The size of the large high gloss plate was 300*150*3 mm, and "-" represented no fabric pattern, silver wire and other defects, and the more "+" represented the more fabric pattern, silver wire and other defects.

[0071] Table 2 Test Results of the Properties of the Products of Comparative Examples 1-4 and Examples 1-4

[0072]

[0073] By comparing Examples 1-4 and Comparative Examples 1-4, when diphenyl phosphine oxide was added alone, itaconic anhydride was added alone, 1-propyl phosphonic anhydride was added alone, or diphenyl phosphine oxide and itaconic anhydride were added at the same time, the notched impact strength of the obtained composition was low, and the injection molding appearance had more fabric pattern and silver wire defects. After adding phosphonic anhydride compounds, the impact performance of the material could be greatly improved, and the injection molding appearance was also significantly improved. Even when the talc content was 25%, which was a relatively high amount, the impact strength could still be maintained at 30 KJ / m 2The above, and has good tensile strength, tensile modulus and thermal deformation performance, it is shown that the phosphoric acid anhydride compound greatly improves the compatibility of talcum powder and PC, greatly reduces the degradation of talcum powder to PC.

[0074] It is to be understood that the above description is only a example for clearly illustrating the present application, and does not mean that the present application is limited to this. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, it is not necessary and impossible to enumerate all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A talc-reinforced PC / ABS alloy material, characterized in that, It is prepared from raw materials comprising the following parts by mass: 30-70 parts of polycarbonate resin; 10-50 parts of acrylonitrile-butadiene-styrene copolymer; Talc powder 5.0-25 parts; Contains 0.1-4 parts of phosphoric anhydride compounds; Processing aids: 0-5 parts; The phosphoric anhydride compounds are prepared by reacting diphenylphosphine oxide with itaconic anhydride in a solvent.

2. The talc-reinforced PC / ABS alloy material according to claim 1, characterized in that, It is prepared from raw materials comprising the following parts by mass: 40-60 parts of polycarbonate resin; 20-40 parts of acrylonitrile-butadiene-styrene copolymer; 10-20 parts talcum powder; Contains 0.5-2 parts of phosphoric anhydride compounds; Processing aids: 0.5-3.0 parts.

3. The talc-reinforced PC / ABS alloy material according to claim 1, characterized in that, The phosphoric anhydride compounds are prepared by the following method, including the following steps: Diphenylphosphine oxide, itaconic anhydride, and an organic solvent were mixed and stirred to generate a precipitate. The precipitate was then filtered and dried to obtain the phosphoric anhydride compounds.

4. The talc-reinforced PC / ABS alloy material according to claim 3, characterized in that, The molar ratio of diphenylphosphine oxide to itaconic anhydride is 1:1-1.5; and / or The organic solvent is selected from one or more of ethyl acetate, methyl acetate, butyl acetate, phenyl acetate, dichloromethane, and diethyl ether; and / or The amount of organic solvent used is 1-8 times the mass of diphenylphosphine oxide; and / or The reaction time is 20-45 minutes.

5. The talc-reinforced PC / ABS alloy material according to claim 4, characterized in that, The reaction time is 30-40 minutes.

6. The talc-reinforced PC / ABS alloy material according to claim 1, characterized in that, The polycarbonate resin is selected from one or more of aromatic polycarbonates and aliphatic polycarbonates.

7. The talc-reinforced PC / ABS alloy material according to claim 6, characterized in that, The polycarbonate resin is selected from bisphenol A type polycarbonate.

8. The talc-reinforced PC / ABS alloy material according to claim 6, characterized in that, The polycarbonate resin has a melt flow index of 3-65 g / 10 min when tested at 300°C and 1.2 kg.

9. The talc-reinforced PC / ABS alloy material according to claim 8, characterized in that, The melt flow index is 5-50 g / 10 min.

10. The talc-reinforced PC / ABS alloy material according to claim 9, characterized in that, The melt flow index is 7-35 g / 10 min.

11. The talc-reinforced PC / ABS alloy material according to claim 6, characterized in that, The polycarbonate resin is one or more of Wanhua 2100 and Wanhua 2150.

12. The talc-reinforced PC / ABS alloy material according to claim 1, characterized in that, The acrylonitrile-butadiene-styrene copolymer wherein the mass content of butadiene is 10-30%, the mass content of acrylonitrile is 15-35%, and the mass content of styrene is 50-70%.

13. The talc-reinforced PC / ABS alloy material according to claim 12, characterized in that, The acrylonitrile-butadiene-styrene copolymer is one or more of Chimei PA-757 and Chimei PA-747.

14. The talc-reinforced PC / ABS alloy material according to claim 1, characterized in that, The talc powder has a particle size of 1-9 μm.

15. The talc-reinforced PC / ABS alloy material according to claim 14, characterized in that, The talc powder is one or more of Yirui Stone R7 and Yirui Stone 3CA.

16. The talc-reinforced PC / ABS alloy material according to claim 1, characterized in that, The processing aids are selected from one or more combinations of antioxidants, lubricants, toughening agents, compatibilizers, light stabilizers, heat stabilizers, metal passivators, plasticizers, anti-sticking agents, colorants, coupling agents, nucleating agents, foaming agents, antibacterial agents, antifungal agents, acid removers, hydrolysis resistant agents, chain extenders, flow modifiers, matting agents, antistatic agents, reinforcing agents, fillers, antifogging agents, light diffusing agents, infrared absorbers, fluorescent whitening agents, and laser marking agents.

17. The talc-reinforced PC / ABS alloy material according to claim 16, characterized in that, The light stabilizer is selected from ultraviolet absorbers.

18. The talc-reinforced PC / ABS alloy material according to claim 16, characterized in that, The processing aids are selected from one or more of antioxidants, lubricants, and toughening agents.

19. The talc-reinforced PC / ABS alloy material according to claim 18, characterized in that, Based on 0-5 parts of processing aids, the respective amounts of which are 0-0.5 parts of antioxidant, 0-1 part of lubricant, and 0-4 parts of toughening agent; and / or The antioxidant is selected from one or more of hindered phenols, phosphites, thioesters, benzofurans, acryloyl-modified phenols, and hydroxylamine antioxidants; and / or The lubricant is selected from one or more of the following: fatty alcohols, fatty acids, fatty acid esters, lignite waxes, amide waxes, saturated hydrocarbons, and organosilicones; and / or The toughening agent is selected from one or more of the following: methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic polymer, acrylic-silicone rubber toughening agent, ethylene-methyl acrylate, ethylene-butyl acrylate, and ethylene-acrylate-glycidyl methacrylate terpolymer.

20. The talc-reinforced PC / ABS alloy material according to claim 19, characterized in that, The antioxidant is selected from one or more of BASF antioxidants Irganox 1076, Irganox 1010, Irganox 168, Irgafos 126, Irgafos P-EPQ, and Irganox B900.

21. The talc-reinforced PC / ABS alloy material according to claim 19, characterized in that, The organosilicon is selected from polysiloxanes.

22. The talc-reinforced PC / ABS alloy material according to claim 19, characterized in that, The lubricant is pentaerythritol stearate.

23. The talc-reinforced PC / ABS alloy material according to claim 19, characterized in that, The toughening agent is selected from one or more of methyl methacrylate-butadiene-styrene copolymers.

24. The talc-reinforced PC / ABS alloy material according to claim 23, characterized in that, The toughening agent is selected from one or more of EM500 and M711.

25. The method for preparing talc-reinforced PC / ABS alloy material according to any one of claims 1-24, characterized in that, The steps are as follows: Polycarbonate resin, acrylonitrile-butadiene-styrene copolymer, phosphoric anhydride compounds, and processing aids are mixed according to the formula ratio and fed into the main feed port of a twin-screw extruder. At the same time, talc powder is fed into the side feed port. Then, the mixture is melt-extruded and granulated to obtain talc-reinforced PC / ABS alloy material.

26. The preparation method according to claim 25, characterized in that, The temperature of the conveying section of the twin-screw extruder is set to 210-220℃, the temperature of the plasticizing section is set to 225-270℃, and the temperature of the metering section is set to 225-260℃; the screw speed is 200-600 rpm.

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