SU1046251A1 - Process for preparing copolymers for metallization - Google Patents

Description

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The invention relates to the production of plastics, in particular to the preparation of styrene copolymers and. acrylonitrile with butadiene rubber (ABS); intended for metallization.

Plastic products are metallized to give them special technical and operational properties, namely, mechanical strength, weather resistance (due to protection from exposure to UV radiation and atmospheric influences), electrical conductivity, and also for decorative purposes to give them a presentation. Metallized plastic products are much lighter and much cheaper than similar metal products.

The most common method of applying metal coatings on plastic products is chemistically galvanic metallization (XGM). The properties of the metalized products are determined by the strength of the metal to the polymer (metal adhesion to the polymer). When applying a metal coating using the XGM method, a large metal contact area is used. polymer coatings for which the surface of the polymer is etched.As a result of the etching of the polymer surface, micro-roughness / s enabling better adhesion of metal to polymer.

ABS copolymers are heterophasic materials, so they are prone to etching to produce a microrough surface. However, when metallizing ABS copolymers, it is not possible to obtain a coating with an adhesive of more than 1.1 kJ / m, which is insufficient for long-term use of metallized products.

A method of producing copolymers of ABS for metallization is known, including graft copolymerization of styrene and acrylonitrile with butadiene rubber in an emulsion and mixing the graft copolymer latex with 0.5.5, 0 parts by weight latex butadiene rubber Cl.

However, the materials obtained by this method have low fluidity (melt flow index does not exceed 5 g / 10 min), as a result of which the parts cast from them retain large internal stresses, which significantly weakens the adhesion strength of the metallic coating to the surface of the product: casting samples strength to peel 0.9-1.1 kJ / m.

There is also known a method for producing copolymers of ABS for metallization, according to which styrene and acrylonitrile with butadiene are copolymerized.

A rubber resin modified with maleic or fumaric acid is added with rubber in an aqueous emulsion and to the obtained ABS copolymer. Sheets 5 are made from the composition by the method of injection molding. An oil modified resin is obtained by reacting 100 g of an oil resin with 25 g of maleic or fumaric acid at 200-225 ° C for 5 hours. The resin is introduced in an amount of 5-10% of the total weight of the composition, the adhesion strength of the metallic coating to the surface Molded products reaches 1-1.5.

5 However, the need for energy-intensive and long-lasting modification of the petroleum resin does not lead to a noticeable increase in the adhesion of the metal to the surface of the polymer composition.

In addition, a disadvantage of the known methods is the operation of post-polymerising processing of the ABS polymer, which requires additional equipment and energy consumption for mixing.

The closest to the technical essence of the present invention is a method of obtaining copolymers for metallization by co-polymerization of styrene, acrylonitrile and 1-10% of the total mass of the loading of a modifying resin with butadiene rubber in an aqueous emulsion. 2-vinylpyridine is used as a modifier of the hand vinyl compound. The advantage of this method is its single stage. After chemical electroplating nickel plating, the modified copolymer has a continuous 100% metallic coating, the metal adhesion to the polymer is 0.5 kJ / m C3.

However, such metal adhesion to

f polymer is clearly insufficient for successful operation of metallized products.

The aim of the invention is to increase the adhesion of the metallic coating to the polymer.

I

This goal is achieved by the fact that according to the method of obtaining copolymers for metallization, including copolymerization of styrene, acrylonitrile and 1-10% of the total mass of the loading of the modifying vinyl compound with butadiene rubber in an aqueous emulsion, as a modifier, vinyl vinyl compound is non-vinyl. use a derivative of methacrylic or acrylic acid, selected from the group including diethyl and phenylaminoethyl methacrylate, 2-ethylhexyl, bu 5 tyl and nonyl acrylate.

According to the proposed method, the components are taken in the following relationships, wt.% ;:

Styrene 35-54

Acrylonitrile 25-35

Modifying vinyl

connection 1-10

Butadiene

rubber 18-22

The polymerization is carried out in an aqueous emulsion with a ratio of the organic: phase (water module (bath module 1: (2-3)), in the presence of an emulsifier, for example kg of potassium rosin, polymerization initiator, for example potassium persulfate, and a molecular weight regulator, for example, tertiary dodecyl mercaptan.

 1, A reactor with a capacity of 150 liters, chipped by a mixer, heating and cooling jacket and nitrogen supply system, is loaded with 10.2 kg of latex butadiene rubber with a dry residue of 50% {or 5.1 kg per dry product, which is .; Let 20.4 wt.%), 2.0 kg of potassium soap of disproportionate rosin with a concentration of 25% (or 0.5 kg

on dry Product, which is 2 wt.%), 25 g of potassium persulphate (0.1 May.%) f 68.5 kg of water (bath module 1: 3 and stirred for 15 minutes. In the thus prepared aqueous phase load the mixture monomers consisting of 11.65 kg of styrene (46.6 wt.%), 7 kg of acridonitrile (28.0 wt.%), 1.25 kg of diethylaminoethyl methacrylate (DEAEM) (5 wt.%) in which 138 g of tertiary dodecyl mercaptan (0.55 wt.%) —The resulting reaction mixture under emulation under nitrogen atmosphere emulsifies for 2 hours. Then the temperature is raised to and the wire is copolymerized. for 4 h at and for 5-6 h at a temperature. At the end of the copolymerization, the LAN latex is coagulated with a 3% aluminum sulphate solution, the copolymer powder is extracted with water, dried at 70-75 s and granulated on a screw extruder. Copolymer granules are cast and pressed standard samples for testing. XGM is carried out on the cast and pressed samples according to the scheme and mode presented in Table. one.

Table 1

sucij - 50 g / l

Sensitization HC1 80 MP / L

PdClj- SHjO0.25 g / l

HC110 MP / L

ComCuSO 5H205 G / L

KNaC4H40 50 G / L

NajCOj4 g / L

NSNO10 G / L

NaOH, .10 G / L

Stabilizer1 mp / l

Electrochemical copper plating (40-50 micron layer)

CuSOj,

Hjso

25

25

25

15-20

200 G / L

25

30, 50 G / L The copolymer's ability to metallize is estimated by the amount of metal adhesion to the cast and pressed specimens, which is defined as the RH necessary to peel a 10 mm wide stripe of the metal coating at a right angle at a speed of 20 mm / min (kJ / m L Example 2, the process is carried out analogously to example 1, but DEAEM takes 1 wt.%. Example 3. The process is carried out analogously to example 1, but DEAEM takes 10 wt.%. Example 4. The process is carried out analogously to example 1, but phenylaminoethyl methacrylate is used as a modifying vinyl monomer (PHAM) in an amount of 1 wt.%. Example 5. The process is carried out analogously to example 1, but FAAM is taken in an amount of 5 mao.%. Example 6. The process is carried out analogously to example 1, but FAAM is taken in an amount of 10 wt.%. Example 7. The process is carried out analogously to example 1, but 2-ethylhexyl acrylate (2-EGA) in an amount of 5 wt.% Is taken as modifying vinyl monomer. Example 8. The process is carried out analogously to example 1, but butyl acrylate is taken as modifying vinyl monomer (BA in the amount of 5 May.%. Example 9 The process is carried out analogously to example 1, but nonyl acrylate is taken as the modifying vinyl monomer (HA in the amount of 5 maa.%. Example 10 (control). The process is carried out analogously to example 1 but in the absence of the modifying vinyl monomer. The content was 51 , 6%. The loading formulation and the physicomechanical properties of the copolymers are given in Table 2.

f,

n Ef W C o m M 9.0. In Table 2, it can be seen that modifying ABS copolymers with comonomers leads to a noticeable deterioration of the adhesion of the metal coating to the polymer, without compromising the physicomechanical properties of the copolymer.

Claims (1)

METHOD FOR PRODUCING COPOLYMERS FOR METALLIZATION by copolymerization of styrene, acrylonitrile and 1-10% of the total loading mass of a modifying vinyl compound with butadiene rubber in an aqueous emulsion, characterized in that, in order to increase the adhesion of the metal coating to the polymer, a modifying vinyl compound is used methacrylic or acrylic acid selected from the group consisting of diethyl and phenylaminoethyl methacrylate, 2-ethylhexyl, butyl and nonyl acrylate. _c >