CN108003588B

CN108003588B - High-strength electroplating PC/ABS alloy material and preparation method thereof

Info

Publication number: CN108003588B
Application number: CN201711174102.5A
Authority: CN
Inventors: 邵成华; 蒋斌; 孙阳; 罗明华; 辛敏琦
Original assignee: Shanghai Kumho Sunny Plastics Co Ltd
Current assignee: Shanghai Kumho Sunny Plastics Co Ltd
Priority date: 2017-11-22
Filing date: 2017-11-22
Publication date: 2020-10-30
Anticipated expiration: 2037-11-22
Also published as: CN108003588A

Abstract

The invention relates to a high-strength electroplating PC/ABS alloy material and a preparation method thereof, wherein the alloy material comprises the following components in parts by weight: 50-80% of polycarbonate, 5-50% of SAN master batch containing DMF, 15-40% of polybutadiene rubber powder and 0.4-1% of antioxidant, wherein the SAN master batch containing DMF is prepared by jointly extruding and granulating SAN and DMF, the mass content of DMF is 1-4%, and the alloy material is prepared by firstly mixing in a high-speed mixer, then performing melt extrusion and granulation. Compared with the prior art, the method introduces the DMF solvent which can slightly swell the PC, and can effectively improve the coarsening efficiency of the PC/ABS material in the subsequent processing process, thereby bringing higher plating capacity and electroplating yield.

Description

High-strength electroplating PC/ABS alloy material and preparation method thereof

Technical Field

The invention belongs to the technical field of high polymer materials, and relates to a high-strength electroplating PC/ABS alloy material and a preparation method thereof.

Background

Polycarbonate (PC), a common type of engineering plastic, has excellent rigidity and toughness because it has both a rigid benzene ring and a flexible carbonate bond in its structure. But also suffer from physical disadvantages such as poor flow, notch sensitivity and thick wall sensitivity. For these problems, it is a common practice to blend PC with other materials, especially PC/ABS materials composed of ABS, which can make up for the deficiencies well, have significant advantages in mechanical properties and processability, and become a favored engineering plastic for the industries of automobiles, home appliances, and the like.

Among many applications of PC/ABS, one is used as a plating material and plays a role in household appliances, automobile interior and exterior trims and the like.

According to the electroplating principle, rubber in the material needs to be etched, so that a large number of holes are formed, and subsequent sensitization and activation and chemical nickel plating or copper plating are facilitated. Therefore, generally, the rubber content in the electroplating-grade PC/ABS is obviously higher than that of the common-grade PC/ABS, and meanwhile, the content of the PC is designed to be low, so that the electroplating material can be ensured to have good plating capability and electroplating bonding force.

However, the plated PC/ABS applied to the automobile is mainly processed into two types of parts, one is a plated decoration such as a decoration strip, a label, etc., and the other is a functional part such as a door handle, an air outlet dial wheel, etc. As previously mentioned, typical electroplating grade PC/ABS formulations are designed to have a high gum content and a relatively low PC content in order to ensure electroplating performance. The strength of the PC/ABS material is provided by PC, and the performance of the material can be improved remarkably only when the PC is in a main phase. It can be said that the current mainstream plated PC/ABS is more designed for decorative parts, and when applied to functional parts such as door handles, the strength is relatively insufficient. This is also the reason why many door handles fail after being subjected to a pull test or a fatigue test.

Therefore, how to ensure the plating capacity of the material while increasing the content of PC becomes a problem that many material manufacturers are eagerly to solve.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a high-strength electroplating PC/ABS alloy material and a preparation method thereof.

The purpose of the invention can be realized by the following technical scheme:

a high-strength electroplating PC/ABS alloy material comprises the following components in parts by weight:

wherein the mass content of DMF in the DMF-containing SAN master batch is 1-4%.

Preferably, the alloy material consists of the following components in parts by weight:

wherein the mass content of DMF in the DMF-containing SAN master batch is 2-3%.

The addition of DMF can well promote the swelling of PC, so that the surface of the material becomes slightly loose, thereby promoting the achievement of the roughening process and ensuring that the anchoring holes of the roughened blank piece are more uniform and dense.

Preferably, the polycarbonate is bisphenol A polycarbonate with viscosity average molecular weight of 20000-30000 g/mol.

Preferably, the SAN master batch containing DMF is prepared by jointly extruding and granulating SAN and DMF.

Preferably, the viscosity average molecular weight of the SAN is 100000-200000 g/mol, and the mass content of acrylonitrile in the SAN is 24-30% by weight percentage.

Preferably, the preparation of the DMF-containing SAN masterbatch comprises the following steps:

and (2) placing SAN and DMF in a high-speed mixer, mixing for 10-20 min to obtain a mixed material, putting the mixed material in a double-screw extruder, controlling the rotating speed of the screw to be 180-600 rpm, and performing melt extrusion and granulation to obtain the SAN master batch containing DMF.

Preferably, the viscosity average molecular weight of the polybutadiene rubber powder is 100000-200000 g/mol, and the rubber content is 50-60%.

The reason why the molecular weight range is preferable is that the material has a polycarbonate as the main phase and is a component that provides the strength and fatigue resistance of the material, and the higher molecular weight of PC effectively improves the fatigue resistance of the material. SAN as the dispersed phase, the relatively low molecular weight can provide better flow properties without significantly affecting fatigue resistance. The molecular weight of the polybutadiene rubber powder is in the interval, and the continuous entanglement degree of the polybutadiene rubber powder is more beneficial to coarsening of the material.

Preferably, the antioxidant is one or a mixture of several commercially available antioxidants Irganox1010, Irganox1076 and Irganox 168.

The combination of these antioxidants is chosen primarily for two reasons: one is due to the good compatibility of 1010 and 1076 with PC/ABS materials, and the other is the desire to provide a more comprehensive and integrated protection of the material during extrusion, injection molding and long term use through the combined action of primary and secondary resistances.

The preparation method of the high-strength electroplating PC/ABS alloy material comprises the following steps:

adding the SAN master batch containing DMF, polycarbonate, polybutadiene rubber powder and an antioxidant into a mixer together, mixing for 10-20 min to obtain a mixed material, putting the mixed material into a double-screw extruder, controlling the rotating speed of a screw to be 180-600 rpm, and performing melt extrusion and granulation to obtain the strength electroplating PC/ABS alloy material.

It is clear to engineers who know the electroplating process that the process of electroplating may be subject to a roughening process of the substrate, which is a critical step in determining whether the material can be electroplated well later. At present, for plastic electroplating, the basic process is chemical roughening, namely, the substrate can be oxidized to form more active groups while etching, so that the bonding condition of a subsequent chemical plating layer is enhanced.

In fact, in this process of surface roughening, there are two roughening methods in addition to chemical roughening using strong acid: one is mechanical roughening by means of sand blasting and shot blasting, and the other is swelling roughening by means of a solvent with low solubility. For electroplating solution manufacturers, in actual production, swelling coarsening is put into practical use.

On some electroplating lines needing to be produced in a same line with ABS, if electroplating coarsening and subsequent processes equivalent to ABS are adopted, PC/ABS parts are subjected to one-step pre-coarsening sometimes, which is substantially to swell PC/ABS by adopting solvents such as DMF (dimethyl formamide) and the like so that the surface of the material becomes loose, thereby being beneficial to subsequent etching of strong acid.

Compared with the prior art, the pre-roughening process is creatively and directly introduced into the electroplating PC/ABS material with high PC content. The specific operation is that a DMF solvent capable of slightly swelling PC is introduced in the stage of formula design, and in the subsequent processing process, the addition of DMF can well promote the swelling of PC, so that the surface of the material becomes slightly loose, thereby promoting the achievement of the roughening process, and the anchoring holes of the roughened blank piece are more uniform and dense, thereby bringing higher plating capacity and electroplating yield.

Detailed Description

The present invention will be described in detail with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Example 1

A high-strength electroplating PC/ABS alloy material comprises the following components in percentage by mass:

the preparation method of the alloy material comprises the following steps:

(1) placing SAN and DMF in a high-speed mixer, mixing for 10-20 min to obtain a mixed material, putting the mixed material in a double-screw extruder, controlling the rotating speed of the screw to be 180-600 rpm, and performing melt extrusion and granulation to prepare SAN master batch containing DMF;

(2) adding the SAN master batch containing DMF, polycarbonate, polybutadiene rubber powder and an antioxidant into a mixer together, mixing for 10-20 min to obtain a mixed material, putting the mixed material into a double-screw extruder, controlling the rotating speed of a screw to be 180-600 rpm, performing melt extrusion, and granulating to obtain the high-strength electroplating PC/ABS material.

The characteristics and application of the alloy material of the embodiment are as follows: has higher fluidity and better electroplating binding force, and is suitable for being applied to electroplating pieces such as slender decorative strips and the like. The binding force of the prepared electroplated part is tested by adopting a general GMW14668 method, and the average binding force can reach 7-8N/cm, which is higher than that of the current commercial conventional mark by 5-6N/cm. The melt index reaches 15g/10min under the condition of 260 ℃ and 10kg, and is improved by about 50 percent compared with the main flow mark.

Example 2

the characteristics and application of the alloy material of the embodiment are as follows: has good high temperature resistance and heat resistance stability, and is suitable for being applied to the decoration parts such as electroplated decoration strips, labels and the like on engines. The heat-resistant service temperature of the product prepared by the scheme after electroplating reaches 120 ℃, is increased by about 15 ℃ compared with the common-grade electroplated PC/ABS sold in the market at present, and is more suitable for positions with high heat-resistant requirements such as engine covers.

Example 3

the characteristics and application of the alloy material of the embodiment are as follows: has good strength and fatigue resistance, and is suitable for functional parts such as electroplated inner and outer door handles. The manufactured inner door handle adopts the popular PV3644 pull-out test, and the pull-out strength can reach about 380N under a dynamic method, which is about 30 percent higher than that of the door handle made of common materials. The drawing reciprocating period can reach more than 10 ten thousand times, and is also greatly higher than that of common grade materials.

Example 4

the characteristics and application of the alloy material of the embodiment are as follows: has better heat resistance and strength, and is suitable for being applied to parts with direct sunlight, such as a steering wheel electric plating label and the like. Compared with a same formula control group without DMF, the scheme adopts the same process for electroplating, the electroplating yield is improved by fifteen percent to about 85 percent, and the sample piece prepared by the group without DMF easily has the problem of plating leakage at the edge and corner positions.

Example 5

The high strength plated PC/ABS alloy material of this example is substantially the same as example 1, except that in this example, the composition of the alloy material is as follows:

example 6

example 7

example 8

example 9

in the above embodiments, the polycarbonate is bisphenol A polycarbonate, and the mass content of acrylonitrile in SAN is 24-30%. The rubber content of the polybutadiene rubber powder is 50-60%.

The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims

1. The high-strength electroplating PC/ABS alloy material is characterized by comprising the following components in parts by weight:

wherein the mass content of DMF in the DMF-containing SAN master batch is 1-4%;

the polycarbonate is bisphenol A polycarbonate with the viscosity average molecular weight of 20000-30000 g/mol;

the SAN master batch containing DMF is prepared by jointly extruding and granulating SAN and DMF;

the viscosity average molecular weight of the SAN is 100000-200000 g/mol, and the mass content of acrylonitrile in the SAN is 24-30% in terms of weight percentage;

the preparation of the SAN master batch containing DMF comprises the following steps:

placing SAN and DMF in a high-speed mixer, mixing for 10-20 min to obtain a mixed material, putting the mixed material in a double-screw extruder, controlling the rotating speed of the screw to be 180-600 rpm, and performing melt extrusion and granulation to obtain the SAN master batch containing DMF;

the viscosity average molecular weight of the polybutadiene rubber powder is 100000-200000 g/mol, and the rubber content is 50-60%;

the preparation method of the high-strength electroplating PC/ABS alloy material is characterized by comprising the following steps:

2. The high-strength electroplated PC/ABS alloy material as claimed in claim 1, wherein the antioxidant is one or more of commercially available antioxidants Irganox1010, Irganox1076 and Irganox 168.

3. The method for preparing the high-strength electroplated PC/ABS alloy material as claimed in any one of claims 1 to 2, comprising the following steps: