A coarsening-prone electroplated PC / ABS alloy material, and a preparation method and application thereof

Abstract

The application discloses an easy-coarsening electroplating PC / ABS alloy material and a preparation method and application thereof. The PC / ABS alloy material comprises the following components in parts by weight: 15-80 parts, preferably 20-70 parts, of polycarbonate; 15-70 parts, preferably 20-65 parts, of ABS resin; 1-20 parts, preferably 5-10 parts, of modified polyvinyl alcohol fiber; and 0-3 parts, preferably 0.1-2 parts, of optional processing aids. The modified polyvinyl alcohol fiber is a maleic anhydride grafted modified polyvinyl alcohol fiber. The electroplating PC / ABS material provided by the application has obviously improved coarsening efficiency, and meanwhile, the mechanical properties of the material can be considered.

Description

TECHNICAL FIELD

[0001] The application relates to an alloy material with improved electroplating performance, in particular to an electroplating PC / ABS alloy material easy to be roughened and a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of the automobile industry and the continuous upgrading of the demand for automobile lightweight, electroplating PC / ABS materials are increasingly widely applied to automobile interior and exterior panels, door handles and other parts due to their excellent mechanical properties and the characteristics that excellent metal effects can be obtained after electroplating.

[0003] The specific process of electroplating is relatively complex, mainly including roughening, reduction, sensitization, activation, degelation, chemical nickel plating, pre-plating copper, nickel plating and chrome plating. Among them, roughening is a key step in the pre-treatment process of electroplating. In the electroplating PC / ABS material, the "B" phase butadiene rubber in the ABS material is etched by using chromic acid and concentrated sulfuric acid, so that the material surface presents a micro-rough structure, and the contact area between the plating layer and the plastic matrix is increased. This process endows the PC / ABS material with good electroplating performance. However, PC cannot be electroplated, and the electroplating ability of PC / ABS is not as good as that of ABS. At the same temperature, the roughening time of PC / ABS is longer than that of electroplated ABS. Therefore, it is necessary to develop PC / ABS alloy easy to be roughened to improve the electroplating production efficiency.

[0004] Patent CN103602053A improves the hydrophilicity of the surface of PC / ABS material by adding PEO resin, so that roughening is more likely to occur. However, too low an amount of PEO resin cannot significantly improve the electroplating performance, and too high an amount of PEO resin has a great influence on the compatibility and mechanical properties of the material, and is difficult to be applied to electroplating material application scenarios with high strength requirements. SUMMARY

[0005] In order to solve the above technical problems, the application provides an electroplating PC / ABS alloy material easy to be roughened and a preparation method and application thereof. The electroplating PC / ABS material provided by the application has obviously improved roughening efficiency, and can also consider the mechanical strength of the material.

[0006] To achieve the above purpose, the technical scheme adopted by the application is as follows:

[0007] An electroplating PC / ABS alloy material easy to be roughened, according to weight parts, comprises the following components:

[0008]

[0009] The modified polyvinyl alcohol fiber is a maleic anhydride grafted modified polyvinyl alcohol fiber; preferably, the mass ratio of the modified raw material to the polyvinyl alcohol fiber and maleic anhydride is (5-7):(3-5).

[0010] The content of the modified polyvinyl alcohol fiber in the PC / ABS alloy material is crucial, in order to achieve the present application, the weight of the modified polyvinyl alcohol fiber in the system should be no less than 1 part, preferably no less than 5 parts, otherwise it is difficult to achieve the effect of improving the roughening efficiency, at the same time, the weight of the modified polyvinyl alcohol fiber in the system should be no more than 20 parts, preferably no more than 10 parts, otherwise even if the polyvinyl alcohol fiber is modified by maleic anhydride, it will also affect the toughness and compatibility of the material, and then the mechanical properties will decrease.

[0011] In some specific examples of the present application, the polycarbonate is an aromatic polycarbonate and / or an aliphatic polycarbonate, preferably a bisphenol A type polycarbonate;

[0012] Preferably, the melt flow index of the polycarbonate 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.

[0013] In some specific examples of the present application, the ABS resin is a terpolymer of acrylonitrile, butadiene and styrene, wherein the mass ratio of each component is: acrylonitrile 15-40%, butadiene 10-60%, and styrene 25-70%.

[0014] In some specific examples of the present application, the raw material polyvinyl alcohol used for the polyvinyl alcohol fiber has a polymerization degree of 500-2000 and an alcoholysis degree of more than 50%, preferably 50-95%, and its water-soluble temperature is lower than 60℃, preferably 30-50℃.

[0015] In some specific examples of the present application, the processing aid is selected from one or more of antioxidants, lubricants, light stabilizers, heat stabilizers, antistatic agents, fillers, anti-fogging agents, and light diffusers;

[0016] Preferably, the antioxidant is one or more of hindered phenol, phosphite, thioester, benzofuran, acryl-modified phenol, and hydroxylamine antioxidants;

[0017] Preferably, the lubricant is one or more of fatty alcohols, metal soaps, fatty acids, fatty acid esters, amide waxes, saturated hydrocarbons, polyolefin waxes and their derivatives, organic silicon and silicone powder, and organic fluorine;

[0018] Preferably, the antioxidant is one or more of hindered phenol, phosphite, thioester, benzofuran, acryl-modified phenol, and hydroxylamine antioxidants;

[0019] Preferably, the lubricant is one or more of fatty alcohols, metallic soaps, fatty acids, fatty acid esters, amide waxes, saturated hydrocarbons, polyolefin waxes and derivatives thereof, organosilicon and silicone powder, organofluorine;

[0020] Preferably, the light stabilizer is one or more of benzotriazoles, triazines, benzoic acid esters, cyanoacrylates, phenylimidazoles;

[0021] Preferably, the antistatic agent is one or more of phosphoric acid, inorganic semiconductor salt, carbon black, sodium cellulose sulfate;

[0022] Preferably, the filler is one or more of calcium carbonate, glass fiber, kaolin, silica, talc, montmorillonite, diatomite, barium sulfate, glass microbeads, carbon black, mica, wollastonite, whisker;

[0023] Preferably, the light diffuser is one or more of nano-barium sulfate, calcium carbonate, silica, organic nanometer microbead light diffuser.

[0024] The polyvinyl alcohol fiber in the present application has certain water solubility and hydrophilicity, can efficiently infiltrate in the process of treating the alloy in the roughening liquid, and rapidly forms etching points on the surface of the material for plating combination, thereby improving the plating performance. The maleic anhydride modification retains the hydrophilicity, improves the compatibility of the system by grafting of the anhydride group in the ABS melt co-extrusion process, makes the ABS more uniformly distributed, and is beneficial to roughening. In addition, the introduction of the modified polyvinyl alcohol fiber further improves the mechanical strength of the alloy material.

[0025] A preparation method of the easily roughened electroplating PC / ABS alloy material as described in the foregoing, comprising the following steps: mixing polycarbonate, ABS resin, modified polyvinyl alcohol fiber, optional processing aid and initiator, melt extruding, granulating, and preparing the PC / ABS alloy material;

[0026] Preferably, the initiator is one or both of dicumyl peroxide (DCP) and dibenzoyl peroxide (BPO).

[0027] Preferably, the amount of the initiator is 0.2-0.6% of the total mass of polycarbonate, ABS resin, modified polyvinyl alcohol fiber, and optional processing aid.

[0028] In some specific examples of the preparation method of the present application, the melt extrusion uses a twin-screw extruder, wherein the barrel temperature is 220-260℃, and the screw rotation speed is 200-600 rpm.

[0029] In some specific examples of the preparation method of the application, the preparation method of the modified polyvinyl alcohol fiber is as follows:

[0030] The polyvinyl alcohol fiber, maleic anhydride and esterification catalyst are mixed in a solvent and reacted.

[0031] Preferably, the reaction temperature is 90-100℃, and the reaction time is 8-12h.

[0032] Preferably, the mass ratio of the polyvinyl alcohol fiber to maleic anhydride is (5-7):(3-5).

[0033] In some specific examples of the preparation method of the application, the esterification catalyst is selected from one or more of p-toluenesulfonic acid, sulfurous chloride and trifluoromethanesulfonic acid.

[0034] Preferably, the amount of the esterification catalyst is 0.1-0.3% of the total mass of the polyvinyl alcohol fiber and maleic anhydride.

[0035] Preferably, the solvent is one or more of DMF, dichloromethane and chloroform.

[0036] After the reaction is completed, the reaction solution is cooled, filtered and dried to obtain the modified polyvinyl alcohol fiber.

[0037] The application also provides the use of the easily roughened electroplated PC / ABS alloy material as described above or prepared by the method as described above in automobile parts.

[0038] The PC / ABS alloy material provided by the application has improved roughening efficiency, and after the ABS is grafted with the modified polyvinyl alcohol fiber, the dispersion is more uniform, which can provide more uniform "B" phase for roughening, thereby improving the electroplating quality. In particular, by controlling the component content within a certain range, the application not only does not harm the mechanical properties of the alloy material on the basis of the aforementioned effect improvement, but also has a certain gain effect on the improvement of the mechanical strength. The obtained alloy material is particularly suitable for electroplated material application scenarios with high strength requirements. DETAILED DESCRIPTION

[0039] The application will be further described below through specific examples, and the examples described in the application are only used to illustrate the application and do not limit the scope of the application.

[0040] In the following examples, the information of each raw material is as follows:

[0041] PC 2100: Wanhua Chemical Group Co., Ltd., MFR (300℃ 1.2kg) = 10g / 10min

[0042] PC 2220: Wanhua Chemical Group Co., Ltd., MFR (300℃ 1.2kg) = 22 g / 10 min

[0043] ABS (PA757): Honam, Taiwan, acrylonitrile content 23%, butadiene content 15%, styrene content 62%

[0044] ABS (HR181): Honam, Korea, acrylonitrile content 15%, butadiene content 55%, styrene content 30%

[0045] Maleic anhydride: Shanghai Aladdin Biochem Technology Co., Ltd.

[0046] Polyvinyl alcohol fiber A: 30-45℃ aqueous solution, polyvinyl alcohol degree of polymerization 1700, alcoholysis degree 95%, Shandong Hongsheng New Material Co., Ltd.

[0047] Polyvinyl alcohol fiber B: 70-90℃ aqueous solution, polyvinyl alcohol degree of polymerization 1800, alcoholysis degree 70%, Shandong Hongsheng New Material Co., Ltd.

[0048] Lubricant PETs: Fa Foundation Chemicals (Zhangjiagang) Co., Ltd.

[0049] Antioxidant 1010: Tianjin Li'anlong New Material Co., Ltd.

[0050] Antioxidant 168: Tianjin Li'anlong New Material Co., Ltd.

[0051] Dicumyl peroxide: Shanghai Aladdin Biochem Technology Co., Ltd.

[0052] p-Toluenesulfonic acid: Shanghai Maikelin Biochemical Technology Co., Ltd.

[0053] N,N-Dimethylformamide: Shanghai Aladdin Biochem Technology Co., Ltd.

[0054] Other raw materials and reagents were purchased through commercial channels unless otherwise specified.

[0055] In the following examples and comparative examples, the performance test methods of PC / ABS alloy materials are shown in Table 1:

[0056] Table 1, performance test methods

[0057]

[0058] The processing equipment used includes:

[0059] Double screw extruder, Kobe Long, model ZSK 26Mc 18, length-diameter ratio 52, screw diameter 26 cm;

[0060] Injection molding machine, 130 tons of Krauss Maffei injection molding machine, model KM130-380CX;

[0061] ZWICK Z010TE universal testing machine in Germany;

[0062] ZWICK HIT25P pendulum impact machine in Germany;

[0063] MTS CMT4104-BZ microcomputer control electronic universal testing machine in the United States.

[0064] Example 1

[0065] 50g polyvinyl alcohol fiber A, 50g maleic anhydride and 0.3g p-toluene sulfonic acid were added to 100ml DMF solution, reacted at 90℃ for 8h, filtered, dried at 80℃ for 2h, to obtain modified polyvinyl alcohol fiber 1.

[0066] 19g polycarbonate 2220, 70g ABS (PA757), 10g modified polyvinyl alcohol fiber 1 prepared above, 0.3g lubricant PETs, 0.05g antioxidant 168, 0.05g antioxidant 1010 and 0.6g initiator DCP were added to a high-speed mixer and mixed for 5min. The mixed material was added to the main feeding of a twin-screw extruder, and the extrusion conditions were as follows: screw speed 200rpm, screw temperature from the feeding port to the die was set in sections as follows: 220℃, 225℃, 230℃, 235℃, 235℃, 250℃, 250℃, 245℃, 245℃, 240℃, 240℃. After extrusion, granulation was performed to prepare PC / ABS alloy material.

[0067] Example 2

[0068] 70g polyvinyl alcohol fiber A, 30g maleic anhydride and 0.1g p-toluene sulfonic acid were added to 100ml DMF solution, reacted at 100℃ for 12h, filtered, dried at 80℃ for 2h, to obtain modified polyvinyl alcohol fiber 2.

[0069] 79.4g polycarbonate 2100, 15g ABS (HR181), 5g modified polyvinyl alcohol fiber 2 prepared above, 0.3g lubricant PETs, 0.05g antioxidant 168, 0.05g antioxidant 1010 and 0.2g initiator DCP were added to a high-speed mixer and mixed for 5min. The mixed material was added to the main feeding of a twin-screw extruder, and the extrusion conditions were as follows: screw speed 600rpm, screw temperature from the feeding port to the die was set in sections as follows: 230℃, 235℃, 240℃, 245℃, 250℃, 260℃, 260℃, 255℃, 255℃, 250℃, 250℃. After extrusion, granulation was performed to prepare PC / ABS alloy material.

[0070] Example 3

[0071] Into 100ml DMF solution, 60g polyvinyl alcohol fiber A, 40g maleic anhydride and 0.2g p-toluenesulfonic acid were added, and after reaction at 95℃ for 10h, filtration and drying at 80℃ for 2h, modified polyvinyl alcohol fiber 3 was obtained.

[0072] Into a high-speed mixer, 41g polycarbonate 2100, 50g ABS (HR181), 8g modified polyvinyl alcohol fiber 3 prepared above, 0.4g lubricant PETs, 0.1g antioxidant 168, 0.1g antioxidant 1010 and 0.4g initiator DCP were added and mixed for 5min. The mixed material was added to the main feeding of a twin-screw extruder, and the extrusion conditions were as follows: screw rotation speed 400rpm, screw temperature from the feeding port to the head was set in sections as follows: 235℃, 240℃, 245℃, 250℃, 255℃, 260℃, 255℃, 250℃, 250℃, 250℃. After extrusion, granulation was performed to produce PC / ABS alloy material.

[0073] Example 4

[0074] Into a high-speed mixer, 63g polycarbonate 2100, 30g ABS (PA757), 6g modified polyvinyl alcohol fiber 1 prepared in Example 1, 0.4g talc, 0.3g lubricant PETs, 0.05g antioxidant 168, 0.05g antioxidant 1010 and 0.2g initiator DCP were added and mixed for 5min. The mixed material was added to the main feeding of a twin-screw extruder, and the extrusion conditions were as follows: screw rotation speed 300rpm, screw temperature from the feeding port to the head was set in sections as follows: 220℃, 225℃, 230℃, 235℃, 235℃, 250℃, 250℃, 245℃, 245℃, 240℃, 240℃. After extrusion, granulation was performed to produce PC / ABS alloy material.

[0075] Example 5

[0076] Into a high-speed mixer, 30g polycarbonate 2220, 60g ABS (HR181), 9g modified polyvinyl alcohol fiber 2 prepared in Example 2 above, 0.3g lubricant PETs, 0.1g antioxidant 168, 0.1g antioxidant 1010 and 0.5g initiator DCP were added and mixed for 5min. The mixed material was added to the main feeding of a twin-screw extruder, and the extrusion conditions were as follows: screw rotation speed 500rpm, screw temperature from the feeding port to the head was set in sections as follows: 230℃, 235℃, 240℃, 245℃, 250℃, 260℃, 260℃, 255℃, 255℃, 250℃, 250℃. After extrusion, granulation was performed to produce PC / ABS alloy material.

[0077] Comparative Example 1

[0078] PC / ABS alloy material was prepared according to the same method as in Example 1, except that the modified polyvinyl alcohol fiber in the composition raw material was replaced by polyvinyl alcohol fiber A of the same mass.

[0079]

Comparative Example 2

[0080] PC / ABS alloy material was prepared according to the same method as in Example 1, except that no modified polyvinyl alcohol fiber 1 was added during the preparation process.

[0081]

Comparative Example 3

[0082] PC / ABS alloy material was prepared according to the same method as in Example 1, except that the amount of modified polyvinyl alcohol fiber 1 in the composition raw material was modified to 2 g.

[0083]

Comparative Example 4

[0084] PC / ABS alloy material was prepared according to the same method as in Example 1, except that the modified polyvinyl alcohol fiber 1 in the composition raw material was replaced by a modified fiber prepared by the following method:

[0085] 50 g of polyvinyl alcohol fiber B, 50 g of maleic anhydride, and 0.3 g of p-toluenesulfonic acid were added to 100 ml of DMF solution, and after 8 h of reaction at 90°C, filtration was performed, and drying was performed at 80°C for 2 h to obtain the modified fiber.

[0086] The PC / ABS alloy materials prepared in each example and comparative example were processed into test bars in an injection molding machine, and the screw segment temperatures were set to 230°C, 240°C, 250°C, and 240°C, respectively. The test bars were subjected to the performance tests in Table 2, as follows.

[0087] Table 2, Performance Test Results

[0088]

[0089]

[0090] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the method of the present application, a number of improvements and supplements can also be made, which should be considered as the protection scope of the present application.

Claims

1. An easily roughened electroplated PC / ABS alloy material, characterized in that, By weight, it comprises the following components: 15-80 parts polycarbonate 15-70 parts of ABS resin 5-20 parts of modified polyvinyl alcohol fiber, Optional processing aids 0-3 parts, The modified polyvinyl alcohol fiber is a polyvinyl alcohol fiber grafted with maleic anhydride; the degree of polymerization of the polyvinyl alcohol used in the polyvinyl alcohol fiber is 500-2000, the degree of alcoholysis is more than 50%, and its water solubility temperature is below 60℃. The raw materials used in the PC / ABS alloy material also include an initiator.

2. The easily roughened electroplated PC / ABS alloy material according to claim 1, characterized in that, By weight, it comprises the following components: 20-70 parts polycarbonate; 20-65 parts of ABS resin; 5-10 parts of modified polyvinyl alcohol fiber; Optional processing aids: 0.1-2 parts.

3. The easily roughened electroplated PC / ABS alloy material according to claim 1, characterized in that, The modifying raw material for the modified polyvinyl alcohol fiber, based on the mass ratio of polyvinyl alcohol fiber to maleic anhydride, is (5-7):(3-5).

4. The easily roughened electroplated PC / ABS alloy material according to claim 1, characterized in that, The polycarbonate is an aromatic polycarbonate and / or an aliphatic polycarbonate.

5. The easily roughened electroplated PC / ABS alloy material according to claim 4, characterized in that, The polycarbonate is bisphenol A type polycarbonate.

6. The easily roughened electroplated PC / ABS alloy material according to claim 4, characterized in that, The polycarbonate has a melt flow index of 3-65 g / 10 min at a test temperature of 300°C and a weight of 1.2 kg.

7. The easily roughened electroplated PC / ABS alloy material according to claim 6, characterized in that, The polycarbonate has a melt flow index of 5-50 g / 10 min under test conditions of 300℃ and 1.2 kg.

8. The easily roughened electroplated PC / ABS alloy material according to claim 7, characterized in that, The polycarbonate has a melt flow index of 7-35 g / 10 min under test conditions of 300°C and 1.2 kg.

9. The easily roughened electroplated PC / ABS alloy material according to claim 1, characterized in that, The ABS resin is a terpolymer of acrylonitrile, butadiene, and styrene, wherein the mass percentages of each component are: acrylonitrile 15-40%, butadiene 10-60%, and styrene 25-70%.

10. The easily roughened electroplated PC / ABS alloy material according to any one of claims 1-9, characterized in that, The degree of alcoholysis of the polyvinyl alcohol used in the polyvinyl alcohol fiber is 50-95%, and its water solubility temperature is 30-50℃.

11. The easily roughened electroplated PC / ABS alloy material according to any one of claims 1-9, characterized in that, The processing aid is selected from one or more of antioxidants, lubricants, light stabilizers, heat stabilizers, antistatic agents, fillers, antifogging agents, and light diffusing agents.

12. A method for preparing an easily roughened electroplated PC / ABS alloy material as described in any one of claims 1-11, characterized in that, Includes the following steps: Polycarbonate, ABS resin, modified polyvinyl alcohol fiber, optional processing aids and initiators are mixed, melt-extruded, and granulated to obtain PC / ABS alloy material.

13. The method for preparing easily roughened electroplated PC / ABS alloy material according to claim 12, characterized in that, The initiator is a peroxide initiator.

14. The method for preparing easily roughened electroplated PC / ABS alloy material according to claim 13, characterized in that, The initiator is one or both of dicumyl peroxide and benzoyl peroxide.

15. The method for preparing easily roughened electroplated PC / ABS alloy material according to claim 13, characterized in that, The amount of the initiator is 0.2-0.6% of the total mass of polycarbonate, ABS resin, modified polyvinyl alcohol fiber, and optional processing aids.

16. The method for preparing easily roughened electroplated PC / ABS alloy material according to claim 12, characterized in that, The melt extrusion uses a twin-screw extruder, wherein the barrel temperature is 220-260℃ and the screw speed is 200-600 rpm.

17. The method for preparing easily roughened electroplated PC / ABS alloy material according to any one of claims 12-16, characterized in that, The method for preparing the modified polyvinyl alcohol fiber is as follows: Polyvinyl alcohol fiber, maleic anhydride, and esterification catalyst are mixed in a solvent and reacted.

18. The method for preparing easily roughened electroplated PC / ABS alloy material according to claim 17, characterized in that, The mass ratio of polyvinyl alcohol fiber to maleic anhydride is (5-7):(3-5).

19. The method for preparing easily roughened electroplated PC / ABS alloy material according to claim 17, characterized in that, The reaction temperature is 90-100℃, and the reaction time is 8-12h.

20. The method for preparing easily roughened electroplated PC / ABS alloy material according to claim 17, characterized in that, The esterification catalyst is selected from one or more of p-toluenesulfonic acid, thionyl chloride, and trifluoromethanesulfonic acid.

21. The method for preparing easily roughened electroplated PC / ABS alloy material according to claim 20, characterized in that, The amount of the esterification catalyst used is 0.1-0.3% of the total mass of polyvinyl alcohol fiber and maleic anhydride.

22. The method for preparing easily roughened electroplated PC / ABS alloy material according to claim 20, characterized in that, The solvent is one or more of DMF, dichloromethane, and chloroform.

23. The application of an easily roughened electroplated PC / ABS alloy material as described in any one of claims 1-11 or an easily roughened electroplated PC / ABS alloy material prepared by the method described in any one of claims 12-22 in automotive parts.

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