RU2603152C2 - Envelopment pigment and preparation method thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to envelopment pigments and to technology for production and can be used in paint and composite materials, in production of polymer coatings. Disclosed method of producing an envelopment pigment comprises conducting a singe-step process with combination of steps of preparing a suspension of a stabilised core and polymerisation of a monomer in presence of an initiator. Method includes intensive mixing of pigment or filler in an aqueous acid solution with pH < 7, containing aniline as a monomer and monoalkylphenyl ester of ethylene glycol as a stabiliser, for one hour or more followed by instant introduction into obtained stable suspension of core initiator - ammonium persulphate. Obtained envelopment pigment consists of 10-95 vol% core in form of organic or inorganic particles with a plate, and/or flake and/or needle shape and 5-90 vol% polymer sheel in form of a layer of conducting polymer - acid-doped polyaniline.

EFFECT: invention enables to obtain in one step an envelopment pigment having an active and passive anticorrosive action, as well as high specific electric conductivity.

2 cl, 80 ex

Description

Technical field

The invention relates to shell pigments and to a technology for producing shell pigments used, for example, in the production of polymer composite materials and coatings.

The prior art method

A known method for producing shell pigment using mini-emulsion polymerization (Mahdavian A.R., Sarrafi Y, Shabankareh M. // Polym. Bull. - 2009. - Vol. 63. - P. 329-340). However, this method requires complex hardware design, a large number of intermediate stages and further destruction of the resulting emulsion.

A known method for producing shell pigment, where a conductive polymer is used as a shell, and the copolymer of styrene and butyl acrylate is the core. An aqueous dispersion of a styrene-butyl acrylate copolymer used as a core is preliminarily prepared, followed by the introduction of a monomer and the formation of a polymer shell. (Huang L., Hou W., Liu Z., Zhang Q. // Chinese Science Bulletin. - 2005. - Vol. 50. - No. 10. - P. 971-975). However, this method requires the preliminary preparation of a core — an aqueous dispersion of a copolymer of styrene and butyl acrylate. In addition, the FeSO ₄ · 7H ₂ O + H ₂ O ₂ initiating system used in this method is extremely sensitive to the ratio between the components. In addition, it has a low oxidative potential.

A known method for producing shell pigment, where SiO ₂ acts as a core, and polystyrene as a shell. In suspension

the core, silicon dioxide, heated to 70 degrees, the monomer and initiator are introduced and polymerization is carried out to obtain a shell pigment (Nagao D., Ueno T., Oda D., Konno M. // Colloid Polym. Sci. - 2009. - Vol. 287. - P. 1051-1056). However, this method requires constant monitoring of pH during synthesis and high temperature, which increases energy consumption.

Closest to the alleged invention (prototype) is the method described in Rubinger CPL at al. // J. Mater. Sci. - 2008. - Vol. 43. - P. 3333-3337. A suspension of SiO _{2 is} pre-mixed in a solution of methyl cellulose. Then, the suspension of SiO _{2 is} poured into the reaction vessel and the FeCl ₃ · 6H ₂ O initiator is added to it, the reaction mass is degassed with nitrogen for 30 minutes. Then pyrrole is introduced and polymerization is carried out for 6 hours in a stream of nitrogen and with constant stirring to obtain a precipitate of shell pigment.

The disadvantages of this method are:

- preliminary obtaining a suspension of the nucleus in a separate vessel;

- the use of the initiator FeCl ₃ · 6H ₂ O, having a low oxidative potential, which leads to a low conversion of the monomer;

- obtaining a mixture of products: shell pigment, polymer, core and, as a result, deterioration.

The objective of the invention is to develop a method for producing a shell pigment having an active and passive anticorrosive action, while maintaining a high electrical conductivity, eliminating the preliminary stages in its production.

The problem is achieved in that in the method for producing shell pigment, the production process is carried out in one stage, combining the stage of preparation of the core and polymerization, for which the suspension is prepared by intensively mixing the core of the shell pigment in an aqueous solution of an acid of any nature, providing pH <7, in the presence of a monomer, which is aniline, using ethylene glycol monoalkylphenyl ether as a stabilizer for an hour or more, to obtain we eat a stable suspension of the core directly in the reaction apparatus, followed by the simultaneous introduction of the initiator, which is used as ammonium persulfate, stirring for one hour and holding for 24 hours, and then subjected to filtration, washing and drying.

The best options for implementing the method

Example 1

0.2 g of ethylene glycol monoalkylphenyl ether, 0.28 g of sulfuric acid with a basic substance content of 93% and 0.25 g of aniline are introduced into 50 ml of water with vigorous stirring. The reaction mass (pH = 1.5) is stirred until complete dissolution. Then 5 g of kaolin are introduced into it. The reaction mass is stirred for 1 hour or more to adsorb the monomer on the core. To the suspension obtained with vigorous stirring, 50 ml of an aqueous solution of ammonium persulfate (0.75 g of ammonium persulfate / 49.25 g of water) are simultaneously added. The reaction system is stirred for 1 hour until the formation of shell pigment and then left for a day. The resulting suspension is filtered off, washing first with 200-250 ml of the acid solution used in the synthesis, and then with 200-250 ml of acetone. The resulting shell pigment was dried at a temperature of 60 ° C for 12 hours. The volume content of PANI in the shell pigment is 10% vol.

Example 2

0.2 g of ethylene glycol monoalkylphenyl ether, 0.28 g of phosphoric acid with a basic substance content of 93% and 0.25 g of aniline are introduced into 50 ml of water with vigorous stirring. The reaction mass (pH = 3) is stirred until complete dissolution. Then 5 g of kaolin are introduced into it. The reaction mass is stirred for 1 hour or more to adsorb the monomer on the core. To the suspension obtained with vigorous stirring, 50 ml of an aqueous solution of ammonium persulfate (0.75 g of ammonium persulfate / 49.25 g of water) are simultaneously added. The reaction system is stirred for 1 hour until the formation of shell pigment and then left for a day. After a day of exposure, the suspension is filtered off, washing first with 200-250 ml of the acid solution used in the synthesis, and then with 200-250 ml of acetone. The resulting shell pigment was dried at a temperature of 60 ° C for 12 hours. The volume content of PANI in the shell pigment is 10% vol.

Example 3

0.2 g of ethylene glycol monoalkylphenyl ether, 0.39 g of hydrochloric acid with a basic substance content of 36% and 0.36 g of aniline are introduced into 50 ml of water with vigorous stirring. The reaction mass (pH = 1.8) is stirred until complete dissolution. Then 5 g of kaolin are introduced into it. The reaction mass is stirred for 1 hour or more to adsorb the monomer on the core. To the suspension obtained with vigorous stirring, 50 ml of an aqueous solution of ammonium persulfate (1 g of ammonium persulfate / 49 g of water) are simultaneously added. The reaction system is stirred for 1 hour until the formation of shell pigment and then left for a day. After a day of exposure, the suspension is filtered, washing first with 200-250 ml of the acid solution used in the synthesis, and then 200-250 ml

acetone. The resulting shell pigment was dried at a temperature of 60 ° C for 12 hours. The volume content of PANI in the shell pigment is 10% vol.

Example 4

0.2 g of ethylene glycol monoalkylphenyl ether, 0.325 g of n-toluenesulfonic acid with a basic substance content of 99.9% and 0.175 g of aniline are introduced into 50 ml of water with vigorous stirring. The reaction mass (pH = 2) is stirred until complete dissolution. Then 5 g of kaolin are introduced into it. The reaction mass is stirred for 1 hour or more to adsorb the monomer on the core. To the suspension obtained with vigorous stirring, 50 ml of an aqueous solution of ammonium persulfate (0.525 g of ammonium persulfate / 49.475 g of water) are simultaneously added. The reaction system is stirred for 1 hour until the formation of shell pigment and then left for a day. After a day of exposure, the suspension is filtered off, washing first with 200-250 ml of the acid solution used in the synthesis, and then with 200-250 ml of acetone. The resulting shell pigment was dried at a temperature of 60 ° C for 12 hours. The volume content of PANI in the shell pigment is 10% vol.

Example 5

0.2 g of ethylene glycol monoalkylphenyl ether, 0.28 g of acetic acid with a basic substance content of 70% and 0.304 g of aniline are introduced into 50 ml of water with vigorous stirring. The reaction mass (pH = 3.2) is stirred until complete dissolution. Then 5 g of kaolin are introduced into it. The reaction mass is stirred for 1 hour or more to adsorb the monomer on the core. To the suspension obtained with vigorous stirring, 50 ml of an aqueous solution of ammonium persulfate (0.91 g of ammonium persulfate /

49.09 g of water). The reaction system is stirred for 1 hour until the formation of shell pigment and then left for a day. After a day of exposure, the suspension is filtered off, washing first with 200-250 ml of the acid solution used in the synthesis, and then with 200-250 ml of acetone. The resulting shell pigment was dried at a temperature of 60 ° C for 12 hours. The volume content of PANI in the shell pigment is 10% vol.

Achievable technical result by the method:

- obtaining in one stage a shell pigment with active and passive anticorrosive action without deteriorating the electrical conductivity.

BACKGROUND OF THE INVENTION

Known structures, the core of which is nanosized iron oxide, and zinc oxide is used as a shell. Iron oxide Fe ₃ O ₄ can be the basis of magnetic materials that have the prospect of use in recording and storage systems. Optically active ZnO, promising for optoelectronics, photocatalysis. Obtaining particles combining these properties will expand the scope of materials based on them. However, such pigments do not possess anticorrosive properties (Chaliapina A.Ya. et al. // Vestnik MITT. - 2011. - T. 6. - No. 6. - pp. 102-104).

Shell pigments are known in which the core is a red iron oxide pigment, and the shell is ammonium iron phosphate (Patent No. 2456316 Russian Federation, IPC C09C 1/22. A method for producing a pigment containing iron phosphate / I.A. Shubenin, E.A. Indeykin. - published on July 20, 2012. - Bulletin No. 20). However, this pigment does not exhibit any passive anticorrosive action and has low electrical conductivity.

A variety of shell pigments are pearl pigments based on mica, specially prepared particles of which are the core for the shell of titanium dioxide or other oxides (Ermilov P.I., Indeykin E.A., Tolmachev I.A. Pigments and pigmented paints and varnishes. - L. : Chemistry, 1987.p. 75-76). Such pigments are able to have a passive anticorrosive effect, but do not have any active anticorrosive effect, and also have low electrical conductivity.

Known structures in which inorganic particles are used as the core, and the shell are polymethylmethacrylate, polystyrene, etc. (Wei S. at al. // J. Polym. Res. - 2011. - No. 18. - p. 125-130. , Zhang Y. at al. // Colloid Polym. Sci. - 2007 .-- Vol. 285. - p. 1061-1066). However, such pigments have neither active nor passive anticorrosive effects and have low electrical conductivity.

Known shell pigment is the main lead silico chromate (3PbO · SiO ₂ · PbO · PbCrO ₄ ). The core of this pigment is SiO ₂ , and lead chromate acts as a shell (Belenky EF et al. Chemistry and technology of pigments. - L .: Chemistry, 1974, p. 366-368). This pigment has good anticorrosive properties in the composition of both organically soluble and water-dispersed paints and varnishes. However, this pigment does not have passive anticorrosive properties, expressed in an increase in the diffusion path of corrosive agents. In addition, the presence of lead in it and chromate ions determine the high toxicity of this pigment, which is unacceptable for use in modern paints and varnishes. In addition, the pigment has a low electrical conductivity.

Closest to the proposed invention (prototype) is a shell pigment, which is a core of silicon dioxide, coated with a shell of polypyrrole (Rubinger CPL at al. // J. Mater. Sci. - 2008. - Vol. 43. - P. 3333 -3337). Such pigments have high electrical conductivity, but it is impossible to achieve a passive and active anticorrosive effect with the help of such pigments.

The objective of the invention is to obtain a pigment with an active and passive anticorrosive action, while maintaining a high electrical conductivity.

The objective is achieved in that, unlike the prototype, particles of various nature (organic or inorganic), lamellar, and / or scaly, and / or needle-shaped are used as a core, and a layer of a conductive polymer PANI doped with various acids is used as a shell, for example, sulfuric, hydrochloric, phosphoric acids, etc. The volumetric content of PANI in such a pigment was from 5 to 90%, and the nucleus from 95 to 10% vol.

Assessment of the anticorrosive properties of shell pigments was carried out by the potentiostatic method. A 3% aqueous solution of sodium chloride was used as a corrosive medium. Corrosion currents were calculated according to the methodology (Standard Practice for Conventions Applicable to Electrochemical Measurements in Corrosion Testing. Standard ASTM G-3, 2004).

The best examples of shell pigments

Example 6

Analogously to example 1, but taken 0.14 g of sulfuric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). The volume content of PANI in the shell pigment is 5% vol.

Example 7

Analogously to example 1, but taken 0.14 g of sulfuric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 5% vol.

Example 8

Analogously to example 1, but taken 0.14 g of sulfuric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 9

Analogously to example 1, but taken 0.14 g of sulfuric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 10

Analogously to example 1, but taken 0.14 g of sulfuric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 5% vol.

Example 11

Analogously to example 2, but taken 0.14 g of phosphoric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). The volume content of PANI in the shell pigment is 5% vol.

Example 12

Analogously to example 2, but taken 0.14 g of phosphoric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 5% vol.

Example 13

Analogously to example 2, but taken 0.14 g of phosphoric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 14

Analogously to example 2, but taken 0.14 g of phosphoric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 15

Analogously to example 2, but taken 0.14 g of phosphoric acid with a basic substance content of 93% and 0.125 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.375 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 5% vol.

Example 16

Analogously to example 3, but taken 0.195 g of hydrochloric acid with a basic substance content of 36% and 0.18 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.5 g of ammonium persulfate / 49.5 g of water). The volume content of PANI in the shell pigment is 5% vol.

Example 17

Analogously to example 3, but taken 0.195 g of hydrochloric acid with a basic substance content of 36% and 0.18 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.5 g of ammonium persulfate / 49.5 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 5% vol.

Example 18

Analogously to example 3, but taken 0.195 g of hydrochloric acid with a basic substance content of 36% and 0.18 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.5 g of ammonium persulfate / 49.5 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 19

Analogously to example 3, but taken 0.195 g of hydrochloric acid with a basic substance content of 36% and 0.18 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.5 g of ammonium persulfate / 49.5 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 20

Analogously to example 3, but taken 0.195 g of hydrochloric acid with a basic substance content of 36% and 0.18 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.5 g of ammonium persulfate / 49.5 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 5% vol.

Example 21

Analogously to example 4, but taken 0.16 g of n-toluenesulfonic acid with a basic substance content of 99.9% and 0.09 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.26 g of ammonium persulfate / 49.625 g of water). The volume content of PANI in the shell pigment is 5% vol.

Example 22

Analogously to example 4, but taken 0.16 g of n-toluenesulfonic acid with a basic substance content of 99.9% and 0.09 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.26 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 5% vol.

Example 23

Analogously to example 4, but taken 0.16 g of n-toluenesulfonic acid with a basic substance content of 99.9% and 0.09 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.26 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 24

Analogously to example 4, but taken 0.16 g of n-toluenesulfonic acid with a basic substance content of 99.9% and 0.09 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.26 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 25

Analogously to example 4, but taken 0.16 g of n-toluenesulfonic acid with a basic substance content of 99.9% and 0.09 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.26 g of ammonium persulfate / 49.625 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 5% vol.

Example 26

Analogously to example 5, but taken 0.28 g of acetic acid with a basic substance content of 70% and 0.15 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.45 g of ammonium persulfate / 49.55 g of water). The volume content of PANI in the shell pigment is 5% vol.

Example 27

Analogously to example 5, but taken 0.28 g of acetic acid with a basic substance content of 70% and 0.15 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.45 g of ammonium persulfate / 49.55 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 5% vol.

Example 28

Analogously to example 5, but taken 0.28 g of acetic acid with a basic substance content of 70% and 0.15 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.45 g of ammonium persulfate / 49.55 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 29

Analogously to example 5, but taken 0.28 g of acetic acid with a basic substance content of 70% and 0.15 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.45 g of ammonium persulfate / 49.55 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 5% vol.

Example 30

Analogously to example 5, but taken 0.28 g of acetic acid with a basic substance content of 70% and 0.15 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (0.45 g of ammonium persulfate / 49.55 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 5% vol.

Example 31

Analogously to example 1, but taken 1.4 g of sulfuric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). The volume content of PANI in the shell pigment is 50% vol.

Example 32

Analogously to example 1, but taken 1.4 g of sulfuric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 50% vol.

Example 33

Analogously to example 1, but taken 1.4 g of sulfuric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 34

Analogously to example 1, but taken 1.4 g of sulfuric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 35

Analogously to example 1, but taken 1.4 g of sulfuric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 50% vol.

Example 36

Analogously to example 2, but taken 1.4 g of phosphoric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). The volume content of PANI in the shell pigment is 50% vol.

Example 37

Analogously to example 2, but taken 1.4 g of phosphoric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 50% vol.

Example 38

Analogously to example 2, but taken 1.4 g of phosphoric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 39

Analogously to example 2, but taken 1.4 g of phosphoric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 40

Analogously to example 2, but taken 1.4 g of phosphoric acid with a basic substance content of 93% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (3.75 g of ammonium persulfate / 46.25 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 50% vol.

Example 41

Analogously to example 3, but 1.95 g of hydrochloric acid is taken with a basic substance content of 36% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (5 g of ammonium persulfate / 45 g of water). The volume content of PANI in the shell pigment is 50% vol.

Example 42

Analogously to example 3, but 1.95 g of hydrochloric acid is taken with a basic substance content of 36% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (5 g of ammonium persulfate / 45 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 50% vol.

Example 43

Analogously to example 3, but 1.95 g of hydrochloric acid is taken with a basic substance content of 36% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (5 g of ammonium persulfate / 45 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 44

Analogously to example 3, but 1.95 g of hydrochloric acid is taken with a basic substance content of 36% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (5 g of ammonium persulfate / 45 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 45

Analogously to example 3, but 1.95 g of hydrochloric acid is taken with a basic substance content of 36% and 1.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (5 g of ammonium persulfate / 45 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 50% vol.

Example 46

Analogously to example 4, but 1.63 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 0.88 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (2.53 g of ammonium persulfate / 47.47 g of water). The volume content of PANI in the shell pigment is 50% vol.

Example 47

Analogously to example 4, but 1.63 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 0.88 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (2.53 g of ammonium persulfate / 47.47 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 50% vol.

Example 48

Analogously to example 4, but 1.63 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 0.88 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (2.53 g of ammonium persulfate / 47.47 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 49

Analogously to example 4, but 1.63 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 0.88 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (2.53 g of ammonium persulfate / 47.47 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 50

Analogously to example 4, but 1.63 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 0.88 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (2.53 g of ammonium persulfate / 47.47 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 50% vol.

Example 51

Analogously to example 5, but taken 1.4 g of acetic acid with a basic substance content of 70% and 1.52 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.56 g of ammonium persulfate / 45.44 g of water). The volume content of PANI in the shell pigment is 50% vol.

Example 52

Analogously to example 5, but taken 1.4 g of acetic acid with a basic substance content of 70% and 1.52 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.56 g of ammonium persulfate / 45.44 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 50% vol.

Example 53

Analogously to example 5, but taken 1.4 g of acetic acid with a basic substance content of 70% and 1.52 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.56 g of ammonium persulfate / 45.44 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 54

Analogously to example 5, but taken 1.4 g of acetic acid with a basic substance content of 70% and 1.52 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.56 g of ammonium persulfate / 45.44 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 50% vol.

Example 55

Analogously to example 5, but taken 1.4 g of acetic acid with a basic substance content of 70% and 1.52 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.56 g of ammonium persulfate / 45.44 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 50% vol.

Example 56

Analogously to example 1, but taken 2.52 g of sulfuric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). The volume content of PANI in the shell pigment is 90% vol.

Example 57

Analogously to example 1, but taken 2.52 g of sulfuric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 90% vol.

Example 58

Analogously to example 1, but taken 2.52 g of sulfuric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 59

Analogously to example 1, but taken 2.52 g of sulfuric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 60

Analogously to example 1, but taken 2.52 g of sulfuric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 90% vol.

Example 61

Analogously to example 2, but taken 2.52 g of phosphoric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). The volume content of PANI in the shell pigment is 90% vol.

Example 62

Analogously to example 2, but taken 2.52 g of phosphoric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 90% vol.

Example 63

Analogously to example 2, but taken 2.52 g of phosphoric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 64

Analogously to example 2, but taken 2.52 g of phosphoric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 65

Analogously to example 2, but taken 2.52 g of phosphoric acid with a basic substance content of 93% and 2.25 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (6.75 g of ammonium persulfate / 43.25 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 90% vol.

Examples 66

Analogously to example 3, but taken 3.51 g of hydrochloric acid with a basic substance content of 36% and 3.24 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (9 g of ammonium persulfate / 41 g of water). The volume content of PANI in the shell pigment is 90% vol.

Example 67

Analogously to example 3, but taken 3.51 g of hydrochloric acid with a basic substance content of 36% and 3.24 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (9 g of ammonium persulfate / 41 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 90% vol.

Example 68

Analogously to example 3, but taken 3.51 g of hydrochloric acid with a basic substance content of 36% and 3.24 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (9 g of ammonium persulfate / 41 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 69

Analogously to example 3, but taken 3.51 g of hydrochloric acid with a basic substance content of 36% and 3.24 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (9 g of ammonium persulfate / 41 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 70

Analogously to example 3, but taken 3.51 g of hydrochloric acid with a basic substance content of 36% and 3.24 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (9 g of ammonium persulfate / 41 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 90% vol.

Example 71

Analogously to example 4, but 2.93 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 1.58 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.73 g of ammonium persulfate / 45.27 g of water). The volume content of PANI in the shell pigment is 90% vol.

Example 72

Analogously to example 4, but 2.93 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 1.58 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.73 g of ammonium persulfate / 45.27 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 90% vol.

Example 73

Analogously to example 4, but 2.93 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 1.58 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.73 g of ammonium persulfate / 45.27 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 74

Analogously to example 4, but 2.93 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 1.58 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.73 g of ammonium persulfate / 45.27 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 75

Analogously to example 4, but 2.93 g of n-toluenesulfonic acid are taken with a basic substance content of 99.9% and 1.58 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (4.73 g of ammonium persulfate / 45.27 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 90% vol.

Example 76

Analogously to example 5, but taken 2.52 g of acetic acid with a basic substance content of 70% and 2.74 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (8.19 g of ammonium persulfate / 41.81 g of water). The volume content of PANI in the shell pigment is 90% vol.

Example 77

Analogously to example 5, but taken 2.52 g of acetic acid with a basic substance content of 70% and 2.74 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (8.19 g of ammonium persulfate / 41.81 g of water). As a core, 5 g of talc are used. The volume content of PANI in the shell pigment is 90% vol.

Example 78

Analogously to example 5, but taken 2.52 g of acetic acid with a basic substance content of 70% and 2.74 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (8.19 g of ammonium persulfate / 41.81 g of water). As a core, 5 g of bentonite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 79

Analogously to example 5, but taken 2.52 g of acetic acid with a basic substance content of 70% and 2.74 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (8.19 g of ammonium persulfate / 41.81 g of water). As a core, 5 g of phlogopite is used. The volume content of PANI in the shell pigment is 90% vol.

Example 80

Analogously to example 5, but taken 2.52 g of acetic acid with a basic substance content of 70% and 2.74 g of aniline and 50 ml of an aqueous solution of ammonium persulfate (8.19 g of ammonium persulfate / 41.81 g of water). As a core, 5 g of a blue phthalocyanine pigment is used. The volume content of PANI in the shell pigment is 90% vol.

46

Achievable technical result on shell pigment

An advantage of the claimed shell pigment are:

- active anticorrosive effect due to the presence of a PANi layer, which catalyzes the oxidation of the metal with the formation of a thin protective layer.

- passive anticorrosive effect due to the use of a core of various nature (organic or inorganic) with lamellar, and / or scaly, and / or needle-shaped particles.

Claims (2)

1. A method of producing a shell pigment, including the preparation of a suspension of a stabilized core, polymerization of a monomer in the presence of an initiator, characterized in that the production process is carried out in one stage, combining the stage of preparation of a suspension of a stabilized core and polymerization, for which the suspension is prepared by intensively mixing the pigment or filler of organic or inorganic nature in an aqueous solution of acid with a pH <7 containing aniline as a monomer and monoalkylphenyl ethylene glycol ether as a stabilizer, for an hour or more, by obtaining a stable suspension of the core directly in the reaction apparatus, followed by simultaneous introduction of the initiator, which is used as ammonium persulfate, stirring for an hour, holding for 24 hours, filtering, washing and drying. 2. Shell pigment obtained by the method according to claim 1, consisting of a core consisting of lamellar and / or scaly and / or needle-shaped particles of organic or inorganic nature, and as a polymer shell, a layer of a conductive polymer - polyaniline doped with acid , in the following ratio of components,% vol .: core 10-95, polymer shell 5-90.