High-heat-resistance polycarbonate / cycloolefin polymer material and preparation method thereof

Abstract

The invention relates to a high-heat-resistance polycarbonate / cycloolefin polymer material and a preparation method thereof. The high-heat-resistance polycarbonate / cycloolefin polymer material comprises the following components in parts by weight: 60-80 parts of polycarbonate resin PC, 20-40 parts of cycloolefin polymer COC, 5-10 parts of a compatilizer, 0.1-1 part of an antioxidant and 0.1-1 part of a lubricant. The preparation method comprises the following steps: mixing the polycarbonate resin PC, the cycloolefin polymer COC, the compatilizer, the antioxidant and the lubricant, and carrying out melt extrusion and granulation. Compared with the prior art, the PC / COC alloy is prepared by modifying and blending the excellent low hygroscopicity and extremely high chemical tolerance of the COC and the PC, the alloy combines the excellent toughness and heat resistance of the PC and the low hygroscopicity and excellent gas barrier property of the COC, and the injection molding silver wire and paint spraying bottom biting performance of the PC can be improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and relates to a high-heat-resistant polycarbonate (PC) / cyclic olefin polymer (COC) material and a preparation method thereof, in particular to a high-heat-resistant polycarbonate / cyclic olefin polymer material with low moisture absorption and high chemical resistance and a preparation method thereof. BACKGROUND

[0002] Polycarbonate resin has excellent impact resistance, heat resistance and transparency, a wide use temperature range, high dimensional stability, good creep resistance, and is widely used in the fields of automobiles, electronic appliances, glass lenses and medical devices. However, polycarbonate is prone to moisture absorption, and injection molding is prone to material flowers, especially when injection molding large-sized parts, the problem is more serious, and the solvent resistance is poor, and stress cracking is prone to occur, which also limits the application of polycarbonate in some occasions or fields.

[0003] Cyclic olefin polymers are applied in optical lenses and packaging fields due to their high heat resistance, high light transmission and excellent chemical resistance. PC / COC alloy can make up for the high moisture absorption of PC, improve the chemical resistance to a certain extent, and maintain the high heat resistance of PC / COC material, solve the common injection molding material flower problem of PC alloy, and improve the paint biting performance of the material.

[0004] The prior art CN107383740A discloses a high-strength and low-shrinkage PP / COC alloy material and a preparation method thereof. The alloy material comprises the following raw materials in parts by weight: 20-80 parts of polypropylene, 20-50 parts of cyclic olefin copolymer, 1-5 parts of a compatibilizer, 1-5 parts of a toughening agent, 0.1-0.5 parts of a dispersing agent, 0.2-0.8 parts of a lubricant and 0.1-0.3 parts of an antioxidant. The PP / COC alloy material has high strength, low shrinkage, good dimensional stability, and has better toughness, corrosion resistance, wear resistance, oil resistance and impact resistance, etc., good forming performance, good processing performance, low cost, high use value; the preparation method of the technical scheme is simple, easy to operate and control, stable in quality, high in production efficiency, low in production cost, and suitable for large-scale industrial production. The cyclic anhydride type compatibilizer, carboxylic acid type compatibilizer, epoxy resin compatibilizer, oxazoline type compatibilizer, imide compatibilizer and isocyanate compatibilizer are used to improve the compatibility of PP and COC. However, PC and COC belong to a completely incompatible system of polarity-nonpolarity, and the above compatibilizers have limited improvement effect on the compatibility of the system, and the toughness is poor, so an external toughening agent is needed, which increases the application cost and limits the application range. SUMMARY

[0005] The application aims to provide a high-heat-resistant polycarbonate / cyclic olefin polymer material with low moisture absorption and high chemical resistance and a preparation method thereof.

[0006] The application aims to provide a high-heat-resistant polycarbonate / cyclic olefin polymer material with low moisture absorption and high chemical resistance and a preparation method thereof.

[0007] The first aspect of the application provides a PC / COC alloy, comprising the following components and weight contents: 60-80 parts of polycarbonate resin PC, 20-40 parts of cyclic olefin polymer COC, 5-10 parts of a compatibilizer, 0.1-1 part of an antioxidant, and 0.1-1 part of a lubricant; the compatibilizer is POE-g-GMA.

[0008] In some specific embodiments, the compatibilizer is SOG-03 type POE-g-GMA.

[0009] In some preferred embodiments, the PC / COC alloy comprises the following components and weight contents: 60-70 parts of polycarbonate resin PC, 25-35 parts of cyclic olefin polymer COC, 5-10 parts of a compatibilizer, 0.5 parts of an antioxidant, and 0.5 parts of a lubricant.

[0010] In some specific embodiments, the polycarbonate resin PC has a melt index of 8-30 g / 10 min under the condition of 300 DEG C / 1.2 kg.

[0011] In some specific embodiments, the cyclic olefin polymer COC has a melt index of 10-40 g / 10 min under the condition of 260 DEG C / 2.16 kg.

[0012] In some preferred embodiments, the cyclic olefin polymer COC is APL6011T type cyclic olefin copolymer.

[0013] In some specific embodiments, the antioxidant is selected from at least one of antioxidant 245, antioxidant 1076, antioxidant 168, or antioxidant 1010.

[0014] In some specific embodiments, the lubricant is selected from at least one of silicone powder, pentaerythritol ester, and ethylene bis-stearyl amide.

[0015] The second aspect of the application provides a preparation method of the PC / COC alloy as described above, comprising: mixing and melt-extruding polycarbonate resin PC, cyclic olefin polymer COC, a compatibilizer, an antioxidant, and a lubricant, and granulating to obtain.

[0016] In some specific embodiments, in the melt extrusion, the extrusion temperature is 200-300℃, and the screw extruder rotation speed is 600-900rpm.

[0017] Compared with the prior art, the application has the following beneficial effects:

[0018] The application utilizes the excellent low hygroscopicity and strong chemical resistance of COC, and modifies and blends PC to prepare a PC / COC alloy. The alloy combines the excellent toughness and heat resistance of PC, and the low hygroscopicity and excellent gas barrier property of COC, and can improve the injection molding silver wire and paint bite performance of PC.

[0019] Unlike the current technical means for improving the injection molding silver wire and paint resistance of PC, the application adds a low hygroscopicity COC material, which fundamentally reduces the hygroscopicity of PC material and secondary hygroscopicity in the injection molding process, avoids the injection molding silver wire, and significantly improves the paint bite performance of large-sized parts. DETAILED DESCRIPTION

[0020] The application will be described in detail below in combination with specific examples. The examples are implemented on the premise of the technical scheme of the application, and detailed implementation modes and specific operation processes are given, but the protection scope of the application is not limited to the following examples.

[0021] In the following examples, if no special description is given for the raw reagents or processing technology, it is indicated that they are all conventional commercially available products or conventional processing technology in the art.

[0022] In the following examples and comparative examples,

[0023] The selected PC is L-1250Y of Japan Teijin Chemical Industry Co., Ltd., and the melt index is 10g / 10min under the test of 300℃ / 1.2kg according to the standard of ASTM D1234; the PC-1220 of Sinopec Hunan Petrochemical Co., Ltd. has a melt index of 20g / 10min under the test of 300℃ / 1.2kg;

[0024] The COC is APL6011T of Japan Mitsubishi Chemical Co., Ltd., and the melt index is 26g / 10min under the test of 260℃ / 2.16kg;

[0025] The compatibilizer 1 is SOG-03 (POE-g-GMA) of Shanghai Jiaiyi Company;

[0026] The compatibilizer 2 is CMG5804 (HDPE-g-MAH) of Shanghai Jiaiyi Company

[0027] The antioxidant is antioxidant 1010 and antioxidant 168 produced by Ciba.

[0028] The lubricant is pentaerythritol stearate PETs from FACI (FACI CHEMICALS (ZANGJIANG) CO., LTD).

[0029] Examples and comparative examples

[0030] A method for preparing a PC / COC alloy with low moisture absorption and excellent chemical resistance, comprising the following steps:

[0031] (a) adding PC resin, COC polymer, compatibilizer, antioxidant and lubricant into a mixing blender for mixing;

[0032] Table 1

[0033]

[0034]

[0035] (b) feeding the mixture obtained in step a into the main feeding port of a twin-screw extruder, blending and granulating, and then melt-extruding, with the temperature of each section of the extruder being 200℃-210℃-220℃-230℃-250℃-260℃-280℃-280℃-260℃-230℃, and the rotation speed of the screw extruder being 800rpm, to obtain the product, i.e. a PC / COC alloy material with excellent performance.

[0036] The samples prepared in the examples and comparative examples were tested according to the relevant ISO standards for sample preparation and testing, and the physical properties were as follows:

[0037] Table 2

[0038]

[0039]

[0040] Saturation water absorption: the water absorption when the mass does not increase with time after being placed in water at 23℃;

[0041] Equilibrium water absorption: the water absorption when the mass does not increase with time after being placed in 23℃ / 50% RH;

[0042] Hot stay silver wire: after the sample is hot-stayed in the injection molding machine barrel at 300 DEG C for 10 min, a standard sample of 150*100*3 mm is injection molded, and the proportion of the surface silver wire area of the sample to the total area of the sample is used to represent the thermal stability of the material. The more stars, the more silver wire area, the worse the thermal stability. Specifically: represents that the silver wire area is not more than 5%, represents that the silver wire area is in the interval (5%, 10%], represents that the silver wire area is in the interval (10%, 20%], represents that the silver wire area is in the interval (20%, 30%], represents that the silver wire area is more than 30%.

[0043] Notch impact strength: tested according to ISO 179 standard, laboratory conditions are 23 DEG C, 50% RH;

[0044] Vicat softening temperature: tested according to ISO 306 standard, the temperature rising rate is 50 DEG C / h, and the load is 5 kg;

[0045] The cracking time after ethyl acetate immersion is used to evaluate the chemical resistance of the material. The longer the time, the better the chemical solvent resistance.

[0046] It can be seen from the results that the PC / COC alloy prepared by the present application has very low water absorption rate, and the low moisture absorption rate can ensure that the material will not be re-hydrated during injection molding, and the injection molded parts will not produce silver wire defects. The PC / COC alloy prepared by the present application also has good notch impact strength and Vicat softening temperature, and actually shows good toughness and heat resistance. It can be seen from the evaluation of the chemical resistance of the material by ethyl acetate immersion that the PC / COC alloy prepared by the present application can be immersed in ethyl acetate for a long time without cracking. When the type or content of the compatibilizer is not within the scope of the present application, the PC / COC material prepared by the present application shows poor chemical resistance or toughness, which cannot meet the actual use requirements.

[0047] The above description of the embodiments is for the convenience of the ordinary skilled person in the art to understand and use the application. Those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described herein to other embodiments without having to go through creative labor. Therefore, the present application is not limited to the above embodiments, and those skilled in the art can make improvements and modifications within the scope of the present application without departing from the scope of the present application.

Claims

1. A PC / COC alloy, characterized in that: The invention comprises the following components and their weight contents: 60-80 parts of polycarbonate resin PC, 20-40 parts of cycloolefin polymer COC, 5-10 parts of compatibilizer, 0.1-1 part of antioxidant, and 0.1-1 part of lubricant; The compatibilizer is POE-g-GMA.

2. The PC / COC alloy according to claim 1, characterized in that The compatibilizer is SOG-03 type POE-g-GMA.

3. The PC / COC alloy according to claim 1, characterized in that The invention comprises the following components and their contents by weight: 60-70 parts of polycarbonate resin PC, 25-35 parts of cycloolefin polymer COC, 5-10 parts of compatibilizer, 0.5 part of antioxidant and 0.5 part of lubricant.

4. The PC / COC alloy according to claim 1, characterized in that The polycarbonate has a melt index of 8-30 g / 10 min at 300° C. / 1.2 kg.

5. The PC / COC alloy according to claim 1, characterized in that The cyclic olefin copolymer has a melt index of 10-40 g / 10 min at 260° C. / 2.16 kg.

6. The PC / COC alloy according to claim 5, characterized in that The cyclic olefin copolymer is APL6011T cyclic olefin copolymer.

7. The PC / COC alloy according to claim 1, characterized in that The antioxidant is selected from at least one of antioxidant 245, antioxidant 1076, antioxidant 168 and antioxidant 1010.

8. The PC / COC alloy according to claim 1, characterized in that The lubricant is selected from at least one of silicone powder, pentaerythritol ester, and ethylene bis stearamide.

9. A method for preparing a PC / COC alloy according to any one of claims 1 to 8, characterized in that: include: The polycarbonate resin PC, cycloolefin polymer COC, a compatibilizer, an antioxidant, and a lubricant are mixed, melt-extruded, and granulated to obtain the product.

10. The method for preparing the PC / COC alloy according to claim 9, wherein: In the melt extrusion, the extrusion temperature is 200-300° C., and the speed of the screw extruder is 600-900 rpm.

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