SU326778A1 - FORMING POLYMER COMPOSITION - Google Patents

Description

The invention relates to the preparation of chemical comyosycin for peelectrolytic precipitation and metals containing various nitrogen-containing substances with basic properties in which the nitrogen atom has a free electron pair. Due to the introduction of nitrogen-containing substances, the surface of the polymer matrix becomes suitable for non-electrolytic deposition of metals, i.e., to obtain metallic coatings without the participation of electricity. The introduction of a chemical compound into the polymer matrix formed by thermoplastic polymers, its ability to precipitate metal without the participation of electricity, greatly facilitates the process of metal deposited and increases the strength of the last scene with the surface on which it is applied.

The invention also relates to the use of vinylpyridip acting as an agent that precipitates a metal without electricity, as one of the components of the composition. The surface of thermoplastic products made from a copolymer containing vppilpyridine is not suitable for non-electrolytic deposition of metals.

from the chemical point of view, polymer blends of NLP polymers, which are used as starting materials and materials for the production of various products made using molding methods, while the term "plastic means the final solid product, which may contain naphtha1elp, plasticizers, stabilizers, nigments and so

Further, i.e., the concept of nlastnk includes the polymer matrix as the main component.

The invention affects only a part of a complex process that is used to deposit metals on plasts using a special electrodeposition technique. Since the process of electroplating, i.e. electrolytic deposited metal, requires the presence of a surface,

metal deposition, electrical conduction is deposited, and plastics in most cases are oriotic insulators and not conducting electrical current, then their own current and the necessary condition for this process is the formation of a layer near the surface of the electrical conductivity. This condition is fulfilled by means of a series of preliminary, prior to the electrodeposition stage, technological operations. The culminating stage of all these operations is the proposed non-electrolytic deposition process, after which the surface acquires the higher electrical conductivity necessary to achieve the final stage of electroplating. The pre-electrodeposition stages may include a condensation stage consisting in etching the surface of the plastic, which will be coated with a metal coating, with acid in a bath.

Etching the surface of the plastic with an acid accelerates the formation of a bond, providing a strong pattern between the nastic and the subsequent non-electrolytic coating. The surface of the plastic, after coordination in the second stage, known by the activation step, is transformed into a surface that has catalytic properties. The activation consists in converting the plastic surface to a catalytic surface by adsorbing the catalyst onto the conditioned surface of the stratum and causes the metal layer to become permanently attached to the plastic surface during non-electrolytic deposition of metal. The best catalysts for this purpose are gold, silver and palladium.

In addition, in some cases, the sensitization stage, also known under the ycKOpeiuiH stage, can be carried out prior to the herd of activation, which means that the plastic is immersed in a solution containing tin, titanium and other reducing agents, resulting in a release on the surface of the plate. There is C1 free metal.

At the stage of non-electrolytic metal deposition, the surface of the plastic, containing the precious metal or its salt, such as nalladi 1 or its chloride, is immersed in vaiyu, which is electrolytic, but contains copper or nickel. In this bath, an autocatalytic reduction reaction occurs. The catalytic effect of the precious metal or its salt is to facilitate the reduction of the metal deposited on the surface plastic and the deposition of the metal on the surface of the plastic. The precious metal atoms adsorbed on the surface of the plastic are gradually covered with a layer of precipitated reduced metal, and the non-electrolytic coating process continues until the desired thickness of the coating (metal layer of 40-10 inches) is reached. After the stage of non-electrolytic deposition on the surface of the plate, an electrolytic method and an metallic coating can be used, using any Standard Electroplating Method.

It should be noted that during the pre-deposition of the metal (non-electrolytic coating), the temperature in each coating cycle must not be higher than

melting or softening plastics.

The successful implementation of electroplating depends to a large extent on the pre-precipitation stages of the pre-deposition.

Using the proposed composition, the bond between the surface of the plastic and the metal layer deposited by the non-electrolytic method is very strong. Besides,

The covering ability of the non-electrolytic deposited metal layer on the plastic substrate. The introduction of chemical compounds precipitating a metal results in a more high-quality plating of the plastic with an electrolytically deposited metal layer, at a lower critical time, temperature, concentration of the used solutions and with a shorter duration of plastic pre-treatment stages, which are electroplating.

The composition of the proposed molding comNO3NCH includes a thermoplastic high polymer matrix and an activating additive —

nitrogen-containing polymer with basic properties, containing at least 3 weight. % nitrogen atoms calculated on the total weight of the nitrogen-containing polymer.

An example of nitrogen-containing additives can

serving as nolivinyryridine, a copolymer of various intrabranyl monomers with each other or the reaction product of a copolymer of styrene and maleic anhydride with dimethylaminopropyllamp. Typically, the content of the activator is 0.1-55% by weight of the full-length

matrices containing less than 7.6% nitrogen without

accounting of nitrogen contained in the activating

additive.

The nitrogen-containing substance can be introduced into the polymer matrix by polymerizing nl of displacement.

By physically displacing a polymer that can not be plated, i.e., a strongly retained metal coating cannot be applied to it, due to its low nitrogen content, it is mixed with a material that has a high nitrogen content, as a result of which the resulting mixture acquires the ability to be paid in an electrolytic manner. . It was found that

polymers containing less than 7.6% nitrogen,

as a rule, can be attributed to the discharge

polymers that cannot be disposed of.

Nrn na use and iolimerizatsii

In the method of introducing the activator, the appropriate amount of nitrogen-containing monomer is copolymerized with the monomer or monomers, the polymerisation of which forms the polymer matrix, resulting in a successful matrix to the required value (more than 7.6 wt.%). The thermoplastic high polymer matrix consists of a sonic polymer of 0.25–25% vinylpyridine myomers, 65–90% of styrene thia monomers, and 5–35% acrnlonitrile. The basis of the thermoplastic matrix polymer may also be a graft copolymer (graft-i-polymer) of 0.25-25 wt. % vinylpyridine, 7-80 weight. % styrene and 3-34 weight. % of acryloiitrile applied to elastomeric yarns of polybutadiene, styrene butadiene soloolmer, or a triple rubber-like-like ethylene, iroiilene and didiclopentadiene sonolpmer, and the weight of elastomeric but-isomers in the grafted copolymer can be composed of strains. In cases where a compound that promotes non-electrolytic metal deposition consists of polymer substances (polymers with a degree of polymerization greater than 20), matrices can be obtained using at least one monomer containing one or more nitrogen atoms having basic properties (i.e. nitrogen atoms possessing at least one free or no-longer pair of electrons). As a result of the polymerization of such a monomer, a linear, thermoplastic, synthetic, organic or hydrophobic polymer matrix can be obtained, which can be shaped into the shape of the product and, after appropriate preparation, a metal layer can be deposited by electrolytic method. A substance capable of precipitating a metal without an electric current is mixed with matrix polymers, which can be taken in solid or latex form, by any approach with a separate method, iairimer, in closed mixers or on rollers. Matrix polymers that are not capable of being plated, are straight for use as polymers, are thermoplastic polymers that can be hard, hard, viscous, but not brittle and brittle, and have good toughness, heat resistance, low temperature, softening and chemical resistance. Among them can be called a triple soiolimer Acrylonitrile, butadiene and styrene (copolymer of LC); copolymers of acrylongr 1la and butadiene; a ternary graft copolymer of LAN with a non-desorbed butadiene monomer (Japanese patent LU 0-42-15771), in which 60-90% of butadiene is converted into a polymer and the graft copolymer contains 15-85% of butadiene units (based on the total weight of the suspended polymer) and 85 -15% acrylopitrile and styrene, in particular, 20- 36% acrylonitrile and 80-64% styrene (by weight of the total styrene and acrylonitrile); copolymer of styrene with acrylonitrile, sometimes acetalpium-type mixers, such as polyformaldehyde or polyoxyethylenes; iolimers of acrylic or methacrylic acid esters based on acrylates; iolistyrol and d) polymers of vinyl yugo type; halfpuff; polymers, ioluchee iri, the interaction of aromatic dioxy compounds, i.e. bisphenols (nanopolymer, bisphenol A), with phosgeium, known as nolicarbopates; iolisulfones; Ionoline nolnamidy (nylon). In all painters where the ABS matrix is a mixture of a copolymer of acrploptril with styrene and butadiene acrylic and nitrile rubber (and so on), such a mixture is considered as the polymer, to which is added a substance capable of producing metal by electrolytic method. For a matrix iolimer containing nitrogen atoms (iarnmer, sonnolmer LAN, polyamides), the content of nitrogen should not exceed 7.6 weight. % (based on the total weight of the matrix polymer) to coxpainiTb its classification as a matrix polymer, and not a substance, called a compound, precipitating a metal in a non-electrolytic way. When using vinylline nidridine as one of the comonoles of copolymers or iridescent iolimers, there is no formal difference between the matrix polymer and the compound that precipitates the metal with a non-electrolytic method. Matrix iolimers can be obtained with free radicals and imerimerizacin, which is carried out in a standard way in a block, solution or granule method. Latexes, which were obtained as matrix polymers, can be converted into solid and powder-like polymers by coagulation, flocculation (precipitation in the form of flakes), filtering and drying. The resulting powdered polymer can be mixed in latex form (in the same composition) with rubber and with antioxidants for it, such as trinonnofeyl phosphite or bisphenols, taken in an amount of approximately 1% by weight of rubber. For flocculation of polymers, mixed latexes of nrnbavl to an unmixed aqueous 1-10% solution of calcium chloride or acetic acid and 170-200 ° F. The resulting flocculated residue (sludge) of the flocculated matrix polymer is cooled to room temperature and the filtered matrix polymer is dried to content moisture in it is not more than 1%. This complete polymer can then be mechanically blended and silvered in a softened, molten state on rollers or in closed mixers with various nigments, and lubricated with other additives required for a lump of nitrogen-containing additives with basic properties that are mixed with matrix iolimers include polyvinyl pyridium; sonolymers and vinylyridine; copolymers of styrene, acre) 1lonitrile and viiiiridine; irivate nolymer, obtained as a result of vrnilnvnn viiilniridina, acrylonitrile and styrene, and on elastomeric values (threads) of nolubutadiene, butadiene hydrochloric monomers (it is desirable that styrene monolimers with butadiene contain less than 40% of styrene and i-siolmers and simulimers of styrene with butadiene contain less than 40% of styrene and i-si-solmers and simulimers of styrene with butadiene contain less than 40% of styrene and i-si-solmers and simulimers of styrene with butadiene contain less than 40% of styrene and i-si-solmers and simulimers of styrene with butadiene contain less than 40% of styrene and i-solimers, and soy solmers less than 40% of styrene and soyolmers and simulimers and less than 40% of styrene and soyolmers and simulimers and less and 40% of styrene and butadiene; methacryloyl; co-polymers of methacrylonitrile, styrene and acrylonitrile; copolymers of a few new anhydride with maleiiimide.

It was found that when introduced into matrix polymers of 0.1-55, preferably up to 45, esh, e is better than 0.5-11 weight. % (based on the total weight of the mixture) of nitrogen-containing, nh polymer, with basic properties, almost the entire surface of the plastic is covered with a layer of non-electrolytically deposited metal. In addition, this achieves, as a rule, much stronger adhesion between the non-electrolytically deposited metal and plastic than that used by already known methods, and plastic turns into a material suitable for electroplating, at lower critical parameters of the preliminary stages of processing.

Generally speaking, the most preferred nitrogen-containing polymer is polyvinylpyridine, which includes viiiniridine homopolymers and co-polymers of various monomers with vinylpyridine derivatives. Viiylpyridine based polymers can be obtained by the emulsioin method (suspension) polymerization, block polymerization, in solution, by the granular method using azobisisobutyronitrile as the initiator and radical polymerization. The intrinsic viscosity η of the vinylniridine polymers used, measured in niridine at 30 ° C, is 0.2-2.

Although polymers of viiylpyridine, as preferred, are easily mixed with full-matrix, i.e., it can be easily inserted into it, sometimes prn etched the surface of an item made of plastic in a sulfuric acid solution of bnhromate, some nolpmer of internal flax-neridine leach (washed), and leftoverly washed out (washed), leftoverly washed out, washed, and washed. To prevent leaching, etching is carried out under ME rigid conditions, for example, using an etching bath for a mild acid etched, and / or using polyvinylpyridine with a higher characteristic viscosity, and / or using copolymers of vinylpyridine with acrylonitrile and styrene.

Vinylniridine co-polymers, styrene with acryloiitrile, or graft polymers obtained by grafting of vinylniridine.

acrylonitrile and styrene on the elastomeric high molecular chains of polybutadiene, a styrene butadiene builder, or an ethylene, propylene n, dicycloientadiene copolymer, are used in such a way that the active element, which facilitates non-electrolytic metal deposition, becomes the business builder, and an architect, as well as an entrepreneur. TC physically

indistinguishable. When desired, copolymer resins and graft polymers can be mixed in any way with two nolmer formed, or a resin and / or graft iolimer can be mixed with any of the ABS nlasts taken in an amount up to 45%. Copolymer resins or graft-iolimers should contain 0.065-2.75% nitrogen atoms (based on the weight of the polymer) supplied by vinylyridine. One of the advantages of using vinylniridine as the integral part of the copolymer or graft polymer is to preserve the structural properties of ABS and plastic as well as rubbers when vinyl pyridium is introduced into them. .

In a copolymer resin, the proportion of acrylonitrile may be 5-35, preferably 20-25%, the proportion of styrene 90-65, preferably 80-65%; dale activator, most often vinylnnidine, 0.25-25, is not preferable

1 - 10%.

In the graft polymer, the acrylonitrile component may be 3-34, preferably 8-30%; styrene component 7-80, often 20-60%, and the proportion of activator

(viiilyiridin, preferably 2-vinyl niridine) 0.25-25, preferably 1 - 10%.

The rubber yarns to which nolybutadiene, butadiene styrene or ethylene nylonylene or cyclopentape end copolymer are grafted can contain 10-90 wt. % grafted polymer, preferably 15-75 weight. %

By the common name styrene is meant a whole range of derivatives of styrene, including

including methystyrene.

It is very important and extremely necessary to achieve as uniform a mixture as possible of the matrix number with the actnvator. To do this, plastic can be rolled out on a roller,

Used in rubber production, at a temperature of rolls of 275-360, preferably 300-330 ° F, mix and apply for 5 minutes. Thermonlastic material removed from rollers may not be used in products

the method of pouring iodine with a pressure at a temperature of 360 ° F or injection (injection) into the ness-form in the molten state at a temperature of the mass to be processed is 375-535 ° F (optimally 410-500 ° F).

For unprocessed products, you can use the extrusion method at a polymer mass temperature of 360-520 ° F (preferably 410-480 ° F). The mixes used in the above nimers were plated on

and then thoroughly mixed in the molten state in closed mixers.

Due to the homogeneous mixing of 0.1 - 55 weight. % (preferably 0.1-45% by weight) of an activator with a matrix polymer or polymers, described above, drying is achieved, a natural improvement in the method of non-electrolytic metal deposition increases the rate of non-electrolytic metal deposition and uniformity of the metal coating, and all this is obtained when after pretreatment, the samples are placed in solutions of nickel or copper salts. The most noticeable and significant improvement is achieved when using nickel salt solutions.

The ability of the polymer matrix to be plated is observed even when the specific gravity of the pickling solution used in the pretreatment stage of the nlastik surface is below the level recommended in accordance with standard etching technology and / or when the non-electrolytic coating is carried out in solutions of which the metal ion is is at a lower level than in standard solutions used in industry for plating.

In addition, using a modified matrix, the adhesion between the metal and the surface of the plastic increases. The strength of the scene is determined by measuring the force required to peel a metallic coating, such as electrolytically deposited copper on non-electrolytic nickel, from the surface of the plastic. For this purpose, apply the method of facing coatings - Jacquet Test.

Example 1. Technique for pretreatment of thermoplast nimerimp materials (ABS copolymer, polyproniles, polyvinyl chloride) before electrolytic precipitation.

Injection-molded sample (2-v / XS-Vs) of ABS plastic, consisting of graph | T-polymer mixture 65 parts of styrene-acrylonntril copolymer (74/26) with a characteristic viscosity of 0.55, measured in DMF , and ABS-Graft-Enolmer (16/50/34), immersed in a pickling solution (AlaCuplex ABF Etchant), an innovative mixture of chromic and seric acids containing 1.4 wt. % The source of hexavalent chromium ions () in such an etching solution is either chromium oxide or some chromium salts, such as potassium bichromate. The temperature of the pickling solution is 135 ° F, the concentration of potassium bichromate is 58.9 ± 0.3 ° Baume, the etching time is 2–3 min. Then the sample is rinsed and immersed for 2 minutes in a 5% activating aqueous solution of palladium chloride (PdCl2) in hydrochloric acid (pH 1.7-2.2). Present in solution

also buffer, stabilizing and comile-forming agents. (The used solution is known for sale under the name MiiCuplex Activator B). The sample is again cleaned and again immersed for 20 seconds at 75 ° F in a 2% aqueous solution of accelerator with a RP of 6.5-8.5, containing sodium sulfate as a reducing agent. This solution, known as the first commercially available name .MaCuplex Accelerator, restores palladium chloride on the surface of the plastic to a free metal base. Then the sample is again cleaned and immersed in a solution designed for non-electrolytic metal precipitation, known by the name MaCiiplex Chemical Nickel n containing one nln of several nnkel zero salts, buffer, stabilizing agents and reducing agents. However, after being spun into this solution on the surface of the sample, no trace of metallic nickel was found. It was not necessary to eject the electrolytic preparation of the pretreated sample by the usual electroplating method. However, in this case there were no positive results.

Only in some cases were there only minor traces of metal on the sample surface. A copolymer, in which from 1H1H1e styrene / vinyl imp idin / acrylonitrile ravio 64.5 / 4 / 31.5, is obtained by polymerization, carried out by irp 150 ° F for 3 hours. The conversion rate is 97-99%.

Recipe nimerizatsonnoy mixture (in weight. H.):

Water 120

Styrene64,5

2-Vinyliyridnn4.0

Acrylonitrile31,5

MTM (mixed Cia-, Ci4-,

S1b-mercaptans) 0.82

Dresnnat-731 (dresinate-sales soap) 2.0 calp persulfate (catalyst) 0.3 Caustic soda (for coitrol pFI) 0.06

Styrene, 2-g And 1ln11rndni n acrnlonntril

carefully stir until a homogeneous mixture is obtained. The soap is replaced with an amount of water that is sufficient for the 6% solution obtained. The remaining water is loaded into the glass reactor along with

15 hours. Mixed monomer mix and 5% of the total amount of soap solution prepared earlier. The remaining amount of monomeric mixture and soap solution over a period of approximately 3 hours is continuously loaded.

to the reactor, located in a bath in which temperature of 150 ° F is maintained.

After loading the entire amount of monomer and soap solution, the reactor is kept in this bath for another 1 hour for a complete stabilized B0x1 solution of calcium chloride, the precipitated precipitate is separated and dried at 160 ° F to a moisture content of less than 1%.

The etching solution, the activator solution and the metal-containing solution used in the and subsequent examples are similar to the corresponding solutions used in example 1.

In some examples, the temperature at which samples were processed in the aforementioned solutions was changed.

Prpmer 2. Samples of ABS plastics, similar to the samples indicated in example 1, are treated as in example 1, with the only difference that they use 6% activator solution, 2.5% accelerator solution and solution designed for non-electrolytic nickel precipitation, 150% is used, and its pH is 5.

Polymer matrix containing (by weight hours): 10 styrene-acrylonitrile-viiyl-pyridium terpolymer (64.5 / 31.5 / 4), 57 in dimethylformamide (DMF) at 30 ° С, 55 styrene-acrylonitrile copolymer ( 74/26),, 55 in DMF at 30 ° C, 35 ABS grafiolnmer (16/50/34), 4.033 pigments and 3.0 sizing, incubated for 30 seconds successively in an etching solution (58.5 ° Bome) at 135 ° F, in an activator solution at 120 ° F and at room temperature in an accelerator solution. The control sample contains all of the listed compounds except the styrene-acrylonitrile-pyridine terpolymer, and the styrene-acrylonitrile (74/26) copolymer has a weight of 65% by weight. h

The degree of non-electrolytic coating of the matr) surface is -1%, s 100%. The adhesion strength of a metal coating to the surface of a plastic product is 6.85 lb / in with a coating layer thickness of 1.5-inch (electrolytic copper coating plus a nickel layer applied by non-electrolytic method).

There is no coating on the control sample.

When using a mixture (in weight parts) of 62 styrene-acrylonitrile copolymer (74/26), AND 0.55 in DMF at 30 ° С, 38 winnpyridin-ABS graft copolymer (8/15/50/28), 4.033 pigments in 3.0 sizing, treated in an etching solution (58.5 ° Baume) for 45 seconds at 135 ° F, for 30 seconds in an activator solution at room temperature and for 30 seconds in an accelerator solution at room temperature, the degree of non-electrolytic nickel coating is 100%; the adhesion strength of the metal layer to the surface of the plastic is 5 lb-in at a layer thickness of 1.1 to 10-inch.

On the control sample containing 38 weight. including ABS graft polymer (16/50/34) obtained under US patent No. 3238275, and the above quantities of styrene-acrylonitrile copolymer (74/26), pigments and sizing, no coating,

Mix (in parts by weight): 100 mixtures of A (65/25) styrene copolymer with acrylonitrile (74/26) and ABS graft polymer (16/50/34), 5 (2-methyl-5-vinylpyridine ), i 0,55

(in pyridine at 30 ° C), 4.033 pigments and 3.0 sizing, treated for 3 minutes in an etching solution (55 ° Baume) at 140 ° F, 3 minutes in an activator solution at room temperature, 1 minute in an accelerator solution at

room temperature and 5 minutes in a solution designed for non-electrolytic nickel plating at 150 ° F.

The degree of coating of the plastic surface with a layer of non-electrolytic nickel is 100%.

On a control sample that does not contain full (2-methyl-5-vinylpyridine), no coating is formed.

Example 4. Wire experience, as in example 3, when processing a mixture containing 100 weight. including a mixture of A (64/35) styrene copolymer with acrylonitrile (74/26) and ABS triple-graft copolymer (16/50/34) and 5 wt. including copolymer of styrene and 2-vinylpyridn

(50/50),, 85 in iiridine ori at a temperature of 30 ° C, the degree of coating the surface of the plastic with a layer of electrolytically deposited nickel is 100%.

A control sample not containing a copolymer of styrene and 2-vinylpyridine is not covered with a layer of nickel.

Prpmer 5. As a polymer matrix using high impact polystyrene, known under the brand name "Styron, with beats.

weighing 1.05, tensile strength 5500-7000 psi. an inch, with a softening temperature of 172-176 ° F, a total softening temperature of 220-240 ° F. The surface treatment of the plastic is carried out as in Example 3.

The composition contains (in weight parts): 100

"Stirona 66, 5.0 copolymer of 2-methyl-5-viiiilyridniya and 2-vinylpyridine (50/50), 4.0

pigment and 3.0 oil lubricant.

Plastic coating surface

a layer of non-electrolytically deposited nickel 100%.

A control sample that does not contain a 2-methyl-5-viiyl 11 11 and 2-vinyl pyridine sonolymer is not covered with a layer of nickel.

Example 6. 100 weight. including iolivinyl chloride, known as Marvinol 7120 (Uniroy & Ncorporation), il -0.38 - 0.25 in nitrobenzene and 25 ° C, 6 wt. including poly- (2-methyl-5-vinylpyridine), t1 0.55 in pyridine at 30 ° C, 4.033 weight. including pigments and 3.0 weight. including oiling plants. The surface treatment of the plastic is carried out as in Example 1, holding the sample for 3 minutes in an etching solution (43 ° Baume) at a temperature of 145 ° F, 3 minutes in an activator solution at 90 ° F, 1 minute in an accelerator solution at room temperature for 5 minutes in a solution of nickel salts. Degree of non-electrolytic coating The adhesion strength of a coating to a new plastic surface is 5 psi. For a control sample that does not contain poly- (2-methyl-5-vinylpyridine), there is no coating. Example 7. Using the conditions of treatment, reagents and methods described in example 6, samples containing 100 weight. including acetal polymer (a thermoplastic resin obtained as a result of the poly-interconnection of aldehydes to compounds with a carbonyl group and consisting of polyoxnmethylene chains (OCH2) of great length), known as "Delrip-100, and 3 wt. including 2-methyl-5-vinylpyridine polymer with ij 0.55 (in pyridine nrn 30 ° C) is immersed in a 10% solution of acetone in water for 1 minute and then treated as in example 6. The degree of non-electrolytic coating of the plastic surface nickel 100%. A sample that does not contain 2-methyl-5-vnnniridine polymer is not covered with a nickel layer. Example 8. Smegivi from 100 weight. including thermoplastic resin PA-based acetobutyrate cellulose, known under the trade name "Tenit, 3 wt. including noli- (2-methyl-5-winnylpyridia) with t 0.55 in niridipe at 30 ° C, and using the method of example 1, the plastic is kept for 5 seconds in an etching solution (59 ° Baume) at 135 ° F, 3 minutes in an activating solution at 100 ° F, 30 seconds in an accelerator solution at room temperature and 5 minutes in a solution containing nickel salts at 150 ° F. The degree of non-electroplating of plastic with nickel metal is 100%. For a sample that does not contain an activator, a very insignificant coating is observed. Example 9. As a polymer matrix, a mixture containing (by weight part): 50 P-1700 polysulfone, 37.5 ABS-graft-polymer (16/50/34) and 12.5 acrylonitrile-2-vinylpyridine copolymer is used styrene (31.5 / 4 / 64.5), g | 0.57 in DMF at 30 ° C. Plastic processing is the same as in Example 1. The degree of non-electrolytic coating of the nlast surface with nickel is 100%. Scientia Strength is 3 psi. For a control sample containing 12.5 wt. including copolymer stnrol-acrylonitrile (74/26),, 2 in DMF at 30 ° C, the specified amount of polysulfone and ABS graftpolymer (16/50/34) and not containing the copolymer of acrylonitron-2-vinylpyridine-styrene (31,5 / 4 / 64,5), no coating. The polysulfone P-1700 used, manufactured by Tennessee Eastman Company, contains repeating units (-0-C-0-0-OS-0-0-) Example 10. As an activator, a compound containing a non-aromatic ring and representing is a product of the interaction of styrene copolymer with maleium digestible (CMA) with dimethylaminoyl ammonium (DMAPA), 8 in xylene at 30 ° C, described in the United States Yao 3048487 and No. 3184309. Shift 100 weight. including the ABS-graft polymer specified in nimer 1, and 4.3 wt. including copolymer CMA, processed DMAPA. The obtained samples are treated for 3 minutes in an etching solution (as in Example 1) at 130 ° F, in an activator solution at room temperature and in an accelerator solution at room temperature, and then 5.1.nn in a solution of nickel salts. Nickel coverage: 100%. Control samples that do not contain an activator are not covered with a metal layer. Example 11. Use a mixture (in wt. H.) Pz 30 of a copolymer of styrene and acrylonitrol (74/26), ii 0,55 in DMF and 30 ° C, 40 ABScraft copolymer containing 80% butadiene and 20% styrene- mixture acrylonitrile (70/30) at a conversion of 75% (Japanese Patent H042-1577), and 30 copolymers of styrene, acrylonitrile, and vinyliyridine (64.5 / 31.5 / 4), il 0.57. The processing technique of the plastic surface is the same as in Example 1. Samples are processed for 1 min in an etching solution (59 ° Bome) at 110 ° F, 30 sec in an activator solution at room temperature, 15 sec in an accelerator solution at room temperature and 5 min in nickel salt solution (non-electrolytic plating) at 150 ° F. The degree of non-electrolytic coating of the nick with a nickel layer is 100%. The adhesion strength of the metal coating to the plastic surface is 10 psi. For a control sample that does not contain a copolymer of styrene, acrylonitrile, and vinyl pyridine, the degree of coverage was 50%. The bond strength of the coating with plastic ravia zero. Example 12. For the grafting of polybutadiene and styrene butadiene with styrene to two different copolymers of acrylonitrile, styrene and 2-vipylnridine in their composition, the method proposed in Example 1 was used, but the monomer mixture and the soap solution were not directly mixed into the reaction vessel. In each case, the butadiene-containing polymer is added to the reaction vessel in a single well. The mixture of the remaining monomers and the soap solution are introduced into the reactor continuously and gradually over a period of 3 hours. Recipe of the reaction mixture (in weight. H.): Water140140 Polybutadiene 50- Butadiene copolymer with styrene-50

15

Styrene

Acrylonitrile

2-Vinylpyridine

Potassium persulphate

Dresinat-731 (soap)

NazCOa

NaHCOa

Example 13. Obtaining a copolymer of acrylonitrile, butadiene, styrene and vnnlniridine (12.7 / 15 / 55.3 / 17) with a higher content of vinylpyridine than in example 12, the method of "bead polymerization.

Formulation (in weight. H.): Polybutadiene (Synpol 8107E) 16.0

Styrene55,3

Acrylonitrile12,7

2-Vinylpyridine17.0

Dicumol peroxide0.1

MTM (as in example 1) 0.5

Antioxidant HV-9410,95

Deionized water 200

Polyvinyl alcohol 0.50

Styrene, acrylonitrile, and 2-vinylniridine are mixed in a glass vessel, polybutadiene is added, and mixed until the rubber is dissolved in my sealant. Dicumol peroxide and a mixture of tertiary mercaptans (MTM) are added to the resulting solution, after which the contents of the glass vessel are transferred to a stainless steel reactor equipped with an efficient stirrer. Annarat purged with nitrogen and closed. After stirring, the reaction mixture is gradually heated. 1 hour after the start of the reaction, the temperature of the reaction mixture is 195 ° F, and the solids content increases to 31.8% (from an initial content of about 22.3%). After cooling the reaction mixture below 150 ° F, the apparatus is opened and the aptioxidant is added, then it is closed again and the stirrer speed is increased to quickly and thoroughly mix the antioxidant with the fornolimer. Having opened the device, blowing nitrogen through the reaction mixture, loading the suspending agent (a solution of polyvinyl alcohol in deionized water), close the apparatus, increase the rotational speed of the small dial to 350 rpm and heat it again. The process lasts 16.5 hours at 195 ° F. After raising the temperature to 270 ° F, stir for another 5 hours. After that, the reaction mixture is cooled, the resulting granules are filtered off, washed thoroughly with water and dried. Get 600 g of dry product.

Part of this substance is treated as in example 15, and paid non-electrolytic method. The entire surface of the used plastic is coated with a metal layer that is deposited in a non-electrolytic manner.

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sixteen

plastic material before peelectrolytic plating.

A plastic sample (2,, 18) molded by melt-injection mode was prepared from a mixture of styrene copolymer with acrplonitrile (74/26), prepared as in Example 1, but in the absence of vinyl graphine monomers with ABSloft polymer. 16/50/34), received on

method described in example 1 (but without vinylpyridia and using 16 parts of acrylonitrile), and immersed in a pickling solution, which is a mixture of chromic n sulfuric acid, in which the amount of ions

hexavalent chromium is about 1.40 wt. % The source of ions is either chromium oxide or chromium salts, for example, potassium dichromate. Sample processing in pickling solution (58.9 ± 3 °

Baume) lasts 2-3 minutes at a temperature of 135 ° F.

Then the plastic sample is rinsed in water and immersed for 2 minutes at room temperature in a 5% aqueous activating solution of palladium chloride (PdCl2) in hydrochloric acid (RP 1.7-2.2) containing, in addition to these components, buffer, stabilizing and comfortably forming agents. Rinse the specimen in water again

and immersed for 20 seconds at 75 ° F in a 2% aqueous solution of an accelerator (pH 6.5-3.5) containing sodium bisulfate as a reducing agent. This solution restores palladium chloride to metallic palladium on the surface of the plastic. The sample is then rinsed again in water and immersed in a solution designed for non-electrolytic metal deposition, containing one or more nickel salts, as well as

buffering, stabilizing and reducing agents.

With electrolytic nlating of the sample using the usual electroplating technique, satisfactory results were not obtained. The metallic coating is either completely absent on the sample surface, or it was extremely insignificant.

Example 15. A sample containing (in

weight. h) 65 triple copolymer 1 styrene-vinylpyridine-acrylonitrile (64.5 / 4 / 31.5), ii 0.57 in DMF, 35 ABS-graft-half-measure (16/50/34), 4.033 pygmitic and 3, 0 sizing agents are treated as indicated in Example 14, but a 6% activator solution, a 2.5% accelerator solution are used, and a solution containing nickel salts is used at 150 ° F and pH 5. Treatment in an etching solution ( 58.5 ° Baume) at 135 ° F lasts 45 seconds,

in the activator solution and in the accelerator solution at room temperature for 30 seconds, respectively.

The degree of coating with electrolytically deposited metallic nickel is 100%. A control sample containing 65 wt. including styrene-acryloyitrile copolymer (74/26), m1 of 0.55 in DMF, the same amounts of ABS-graft nolimer, nigments and sizing, but not containing styrene-vinylirid-yiridine-acrylonntril triple soyolmer, is not covered with a layer of nickel. In the above example, the thermoplastic and the graft component of the ABS nlastika were not obtained as in the irimer 1-14. Example 16. Using the procedure described in example 14, various compositions are tested that are treated for 3 minutes in an etching solution (59.5 ° Baume) at 135 ° F, 3 minutes in an activator at a comet temperature, 1 in an accelerator at room temperature and 5 min in a solution of nickel salts intended for electrolytic deposition at 150 ° F and pH 5. For the composition, it contains 1, it has 100 weight. including styrene-acrylonitrivinylpyridia terpolymer copolymer (64.5 / 31.5 / 4), non-electrolytic steppe coverage 100%. When replacing the specified ternary copolymer and 100 weight. The copolymer stprol-acryloyitrile copolymer (72/28) and the plastic plating were not observed with metal. When using 100 weight. including the graft-polymer acrnlonitrile-butadiene-styrene-viiilniridip (16/45/31/8) and 3 wt. including oil or 100 weight. including copolymer of acrylonptyl-butadiene-styrene (25.5 / 20 / 54.5) and 4 wt. including nigments and lubricants, the degree of ze-nic plating is 100% in each case. When replacing the listed graft-nolimer or soiolpmera and 100 weight. including graft polymer acrylonnthyl-butadiene-styrene (16/45/39) or acrylopitrile-butadiene-styrene-vinyl niridine copolymer (22.5 / 20 / 52.5 / 5), the degree of non-electrolytic coating is O or 75%, respectively. Subject of the Invention , noliolefyp and polyamides, and from an activating additive, characterized in that, in order to ensure the possibility of peelectrolytic deposition of the active metal sublayer for the subsequent galvanic As the activating additive, a nitrogen-containing polymer selected from the group consisting of polyvinylpyridium, a copolymer of various vinylpyridine monomers with each other or the product of styrene-hexane polymer copolymer and small anhydride with dimethylaminoprnlamine in the amount of 0.1 to 55% of the polymer weight in the amount of 0.1 to 55% of the weight of the polymer with an polymer in containing 7.6% of nitrogen, without taking into account the nitrogen contained in the activating additive. 2. A composition according to claim 1, wherein the nitrogen-containing additive can be polymerized in the matrix or mixed with it as a polymer.