Curable composition for applying organic coatings on metallic materials

 

(57) Abstract:

The invention relates to curable coatings and can be used in the Metalworking industry for protection of metal parts products from corrosion. Curable compositions containing salts of titanium, manganese and/or zirconium of the unsaturated olefinic carboxylic acids capable of polymerization, and other unsaturated olefin comonomers and initiator of radical polymerization for applying organic coatings on metallic materials. These non-aqueous metallic coating allow pre-processing of steel materials without the use of chromium with excellent corrosion protection. 2 S. and 4 C.p. f-crystals.

The proposed invention relates to curable compositions for applying organic coatings on metallic materials, and method of production thereof, and to a method of coating on the steel surface.

In the Metalworking industry, especially in the production of cars, and instrument-making industry needed protection of metal parts products from corrosion. For this first known level is ammounium cover exhaust fats. Then sheet parts for bodies, body parts or separate devices and when using the mentioned extraction of fats or oils are subjected to deformation by a deep hood. Then assemble by welding, and/or rolling and/or adhesion, conduct cleanup and pre-corrosion treatment of the surfaces of the parts. Anticorrosive treatment consists of phosphating and, as a rule, chromate, and then on the details put the first layer of paint, often by electrodeposition. Typically, such coating by electrodeposition carried out first, especially in the manufacture of automobile bodies, and put several layers of lacquer.

In recent time for pre-treatment of steel sheets are widely used well-known in the steel industry method (coating on steel surface), where steel sheets treated and immediately wound on the drum. This method simplifies many production processes. When the continuous method of pre-processing and, in this case, the organic coating is widely used in the rolling mill for steel sheets. When such a coating on the leaves may be significant shtykoratiey protection of steel sheets used today by numerous steel surface, for example, galvanized by electropolishing, galvanized by dipping into molten metal, galvanized, alteromonas. Metal, improved strip of this kind is obtained directly after antirust treatment. A good lacquer adhesion and good corrosion protection are important for the quality of cars, or appliances collected from these bands. When the conventional method of pre-processing by a known method, described above, still using chromium products to enhance the adhesion of the lacquer and corrosion protection. Also when using this method, as, for example, alkaline passivation is necessary phosphating steel, zinc, or iron, or steel strips products containing chromic acid, for subsequent passivation, to get the desired anti-corrosive effect. When using these methods of waste water to be treated and remove. Processing chemicals containing chromium (VI) to obtain pre-processed products, their movement and use requires special precautions.

The first stage of the waste water is the selection of products on the basis of the La flushing, this method is known as the "indelible".

Recently developed methods of "indelible" pre-processing without using chromium, which are based on aqueous acidic solution containing fluoride salts of titanium, as well as organic polymers as main components. In addition, the possible presence of metal ions, such as manganese, cobalt, Nickel or zinc, as well as phosphates and silicates. As organic components used complexing polymers, such as polyacrylates or derivatives polyvinyldene. An important task of these complexing polymers is the formation with metal ions complexes, which are stable in the aqueous phase. Such chromium, the system described in the European patents EP 0178020, 0469034 or 0555383. Although the latter methods make possible the use of chromium system with good corrosion protection, but the disadvantage is the use of solutions of very strong acids and high concentrations of fluoride ions.

So, there is a need to improve agent pre-treatment and pre-processing that is done in the and strong acids and high concentrations of fluoride. While the components of the compositions should be in it, preferably in a uniform form to avoid separation of the mixture during the process of receiving, handling, exposure and usage.

The objective of the invention is the proposed solution, as well as getting the polymerized compositions for applying organic coatings on metallic materials, which contain at least one salt of titanium, manganese and/or zirconium and unsaturated olefinic carboxylic acid and at least one other unsaturated olefinic of comonomer, and at least one radical polymerization initiator in the not-water system.

Another object of the proposed invention is a method of obtaining these compositions for applying an organic coating, and a method of coating a steel strip.

As the unsaturated olefin polymerized carboxylic acid to generate the corresponding salts of titanium, manganese or zirconium suitable are all known unsaturated olefinic carboxylic acid capable of Homo - and/or copolymerization of: acrylic acid, methacrylic acid, taconova acid, Rotanova carboxyl group was etherification with an alkyl radical; fumaric acid or complex polyether fumaric acid, reactive macromonomer containing carboxyl groups or mixtures of the aforementioned acids. In the framework of this invention, "macromonomers" understand oligomers or polymers with functional end groups that can be activated via the polymerization reaction. Thus, they are fundamentally, the macromolecular monomers. Typically, these macromonomer contain as an end group of unsaturated hydrocarbons, compounds of carbon, i.e. the group of vinyl, acrylate, methacrylate or sterile.

Additionally, the composition may contain other comonomers capable of copolymerization, for example, hydroxyethylacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, hydroxypropylmethacrylate, hydroxyethylacrylate, hydroxyethylmethacrylate, C1-C8-alkylacrylate or methacrylates, as well as one or more named unsaturated olefinic carboxylic acids in free form, i.e. not in the form of salts. The part of the named hydroxyquinoline of comonomers can also be substituted complex poluation of polyethylene glycol of the unsaturated olefin polymerized carboxylic acids.

Suitable photoinitiators are, for example, benzoin, simple antoinettelouis ether, benzylacetone, for example, benzyldimethylamine, derivatives of acetophenone, for example, dialkylamino or dichloro - and trichloroethene; commercially available photoinitiators are Irgacure 651 and 907 (Firma Ciba Geigy).

In addition, these photoinitiators or, including their proposed composition can also contain free radical initiators type peroxides such as benzyl peroxide or azo compounds, for example, 2,2'-azobisisobutyronitrile. In case of purely thermal conducting polymerization of the composition does not contain photoinitiator.

Proposed curable compositions containing such salts of titanium, manganese and/or zirconium from nenasi, 1-8 wt.%, and the content of one or more comonomers to 90 wt. %, and the content of the initiator 2-10 wt.%.

If the comonomers used alkylacrylate and/or alkyl methacrylates, then be sure to add a certain number of compounds with long alkyl chains, as otherwise the composition cannot long remain homogeneous. In addition, the compositions of this kind demonstrate very low corrosion protection. As a rule, part of alkylacrylate, for example, 2-ethylhexyl acrylate, should be less than 50% relative to carboxybenzoyl and/or hydroxyquinoline of comonomers.

Curable compositions based on salts of titanium, manganese or zirconium, of acrylic or methacrylic acid with other acrylate or the methacrylate comonomers are well known. In the German patent application DE-A-2943566 describes a method for ion structured acrylate synthetic polymers, in which the mixture of monomers contains 0.1 to 50 wt.%, at least one metal salt of polymerized unsaturated carboxylic acid. These compositions are thermally polymerized substance. It is found that the polymers of this kind have a high pace the private polymers.

In the international application WO 89/01952 described colorless transparent polymer material, preferably for optical purposes, which is obtained by radical polymerization of a mixture of monomers, which contains 20 wt.% zirconium compounds(VI)-acrylic.

In European patent application EP-A-518609 described surface-structured film, which is applied on a polymer substrate and which is utverzhdennym coating. For these coatings, solvent, use of the composition of the comonomers that contain other metallically, for example, diacrylate zinc, and capable of photopolymerization.

These examples do not disclose curable composition for applying an organic coating by a known method on the metal materials of the proposed species.

The proposed composition may contain additional additives such as lubricant to facilitate subsequent deformation of steel materials. Moreover, it is important that the additives of this kind do not hinder the process of structuring monomers.

The polymerized organic medium has such a polarity that were possible reaction of component metals in the form of salts on the steel on the real surface contribute to the corrosion protection. Therefore it is important that the proposed compositions possible use of corrosion-resistant materials with a small "ballast", those are components that do not contribute to the corrosion protection. At the same time the agent complexing metal together with metal becomes part of the binder agent in the coating on the steel surface.

Receiving selection of songs may carry two different ways. Salts of titanium, manganese and/or zirconium derived from unsaturated olefinic carboxylic acid by a special technique and then dissolved in the remaining comonomers. In conclusion, add one or more initiators.

In the most preferred method of salt of titanium, manganese and/or zirconium of the unsaturated carboxylic acid get in situ, that is, choose the appropriate carboxylic acid and the corresponding metal oxides, metal hydroxides, metal alcoholate, metal carbonates and/or dicarbonyl compounds of metals dissolved in one or more carboxylic acids, the acid, in this case, heat. This can be removed freely turning alcohols or compounds-carbonyl way to get in composition.

The proposed compositions contain virtually no organic solvents. However, this does not mean that small amounts of alcohols, connections-carbonyl or other volatile organic components produced in small quantities in the process, may not be present in the composition.

The proposed composition in the usual way are applied to the steel sheet in sufficient quantity so that the layer thickness was 0.5-10 μm, preferably 1-3 μm.

The following examples explain in more detail the invention. If no other data, all quantitative data compositions take the weight percentage.

A) Obtaining capable of polymerization compositions for coating.

Example 1

14.3 g of the titanium-isopropyl-orthotitanate in isopropanol, 14.5 g of acrylic acid and 66.9 g hydroxyethylacrylate stirred at room temperature until a homogeneous composition for coating.

Example 2

of 40.9 g of maleic anhydride are suspended in 48,5 g hydroxyethylacrylate, heated to 90oWith and within one hour and stirred at this temperature. Then added 16.3 g of the titanium-isopropy isopropanol.

Example 3

of 37.6 g of maleic anhydride are suspended 44.7 g hydroxyethylacrylate, heated to 90oWith and within one hour and stirred at this temperature. Then add 27,3 g titanium-isopropyl-ortho-titanate for 10 minutes. In conclusion, in vacuum at a pressure of about 50 mbar distilled 9.6 g released isopropanol.

Example 4

of 23.6 g of maleic anhydride are suspended in 70,1 g hydroxyethylacrylate, heated to 60oWith and within one hour and stirred at this temperature. Then add 17.1 g of the titanium-isopropyl-ortho-titanate for 10 minutes. In conclusion, in vacuum at a pressure of about 100 mbar distilled 10.8 g released isopropanol.

Example 5

of 19.6 g of maleic anhydride are suspended in 46,8 g hydroxyethylacrylate, heated to 60oWith and within one hour and stirred at this temperature. To the mixture of 12.0 g of a pentaerythritol-triacrylate. After cooling below 35oC for 10 minutes add to 23.4 g of 70% solution of zirconium-isopropyl-ortho-titanate in isopropanol.

The composition with stirring, cook until smooth and then use.

C) Applying and curing

Before grease is found agent as photoinitiator, and with stirring, cook until smooth.

Composition for coating applied to the steel sheet by centrifugation for 10 seconds, depending on the viscosity, at 500-1000 rpm, and the layer thickness of 1-2 μm. Then irradiated for 3 minutes with an ultraviolet lamp, type Ultra Jet 100, with 100 watts per centimeter length of the light.

In conclusion, the steel sheet within 24 hours tested in a salt spray chamber according to DIN 5002155.

Result

Steel sheet, galvanized as by electropolishing, and immersion in the melt ("Galvalume", "Galfan") demonstrates the complete absence of corrosion.

When using compositions without added metals in most of the observed surface corrosion or darkening. Thus, the proposed anti-corrosion current floor level actions equivalent chromium systems.

1. Curable composition for applying organic coatings on metallic materials, which contains at least one salt of titanium, manganese or zirconium unsaturated olefinic carboxylic acid capable of polymerization, characterized in that dopolnyavshayasya fact, what olefinic unsaturated acid selected from acrylic acid, methacrylic acid, basis of itaconic acid, crotonic acid, maleic acid, complex Palmyra maleic acid, fumaric acid, complex Palmyra fumaric acid, reactive macromonomers containing carboxyamide group, or their salts.

3. The composition according to p. 1, characterized in that it further contains at least one unsaturated olefinic of comonomer.

4. The composition according to p. 3, wherein the comonomers are selected from hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate,1-C8the alkyl(meth)acrylates and/or unsaturated olefinic carboxylic acids under item 2 or mixtures thereof.

5. Composition according to any one of paragraphs. 1-4, characterized in that at least one radical polymerization initiator capable of activation by radiation.

6. Method of coating metal materials, mainly steel strip, galvanized by electropolishing or by immersion in a melt, by cleaning and degreasing, cleaning the surface, applying to the surface of the polymerized compositions, curing, otlichayushiesya points, pasted on the metal material layer thickness of 0.1-10 μm, preferably 0.5 to 5 μm, most preferably 1-3 μm, and the curing is carried out by thermal, photochemical or electron beam polymerization.

 

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FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for preparing vinylene carbonate mixture. Method involves interaction of monohaloethylene carbonate of the formula (II): wherein X means halogen atom with a dehydrohalogenating agent at temperature in the range 40-80°C but preferably at 60°C in organic solvent medium wherein ethylene carbonate is used as an organic solvent. As a dehydrohalogenating agent method involves using amine, in particular, trialkylamine but preferably triethylamine, and monochloroethylene carbonate is used as monohaloethylene carbonate preferably. Interaction is carried out in inert gas atmosphere preferably. Invention provides preparing vinylene carbonate mixture by a simple and economy method with the high content of vinylene carbonate in the end product. Method provides easily isolation of vinylene carbonate from the prepared mixture by distillation off, for example, under vacuum in the film evaporator. Also, invention relates to a crude vinylene carbonate mixture prepared by above described method that is designated as an additive for lithium-ionic batteries as a component of surface coating material as a monomer for preparing polyvinylene carbonate.

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7 cl, 3 ex

Composition makeup // 2277552

FIELD: polymer materials.

SUBSTANCE: invention relates to polymer composition based on binder, namely unsaturated polyether resin or oligoether acrylates, and may be used in medicine, in production of paint and lacquer materials, etc. Composition comprises, wt parts: unsaturated polyether resin or oligoether acrylates or mixtures thereof, 100; polymerization promoter, in particular complex compound prepared by reaction of vanadium derivatives (vanadium pentoxide, ammonium methavanadate, of methavanadic acid) with orthophosphoric acid/water/butanol mixture, 0.3-0.88; polymerization initiator: cumene hydroperoxide, 0.3-0.44; and modifying additives, 0-20.

EFFECT: optimized makeup involving inexpensive, easily available, and highly efficient promoter.

1 tbl, 6 ex

FIELD: rocketry; production of the potting composition for armoring the charge made out of the ballistite propellant.

SUBSTANCE: the invention is pertaining to the field of rocketry and presents the potting composition for armoring the charge made out of the ballistite propellant. The potting composition includes polybutylmethacrylate, butylmethacrylate, methylmethacrylateand in the capacity of the initiator and activator of the hardening - benzoyl peroxide and dimethylaniline. At that polybutylmethacrylate is dissolved in the mixture of butylmethacrylate and methylmetacrylate. The invention ensures manufacture of the qualitative products with the required level of the physical-mechanical and adhesive properties, as well as to reduce smokiness of the gases, and to reduce temperature of the waste gases from 2200°С to 800°С.

EFFECT: the invention ensures manufacture of the qualitative products with the required level of the physical-mechanical and adhesive properties, as well as to reduce smokiness of the gases, and significantly to reduce temperature of the waste gases.

2 tbl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to photoinitiating agents of phenylglyoxylic acid order used in polymerizing compositions to be subjected for hardening. Invention describes a photoinitiating agent of the formula (I): wherein Y means (C3-C12)-alkylene, butenylene, butinylene or (C4-C12)-alkylene that are broken by groups -O- or -NR2- and not following in sequence; R1 means a reactive group of the following order: -OH, -SH, -HR3R4, -(CO)-OH, -(CO)-NH2, -SO3H, -C(R5)=CR6R7, oxiranyl, -O-(CO)-NH-R8-NCO and -O-(CO)-R-(CO)-X; R2 means hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R3 and R4 mean hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R, R and R mean hydrogen atom or methyl; R8 means linear or branched (C4-C12)-alkylene or phenylene; R9 means linear or branched (C1-C16)-alkylene, -CH=CH-, -CH=CH-CH2-, C6-cycloalkylene, phenylene or naphthylene; X, X1 and X2 mean -OH, Cl, -OCH3 or -OC2H5. Also, invention describes a method for synthesis of a photoinitiating agent, polymerizing composition and substrate covered by its. Proposed photoinitiating agent possesses the effective introducing capacity and absence of migration in thermal treatments.

EFFECT: improved and valuable properties of agent.

13 cl, 1 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: composition for coating of optical transparent information carriers is described, the composition being curable by UV radiation and including (A) from 1 to 60% by mass of at least one colloid oxide of metal, (B) from 0.1 to 50% by mass of at least one silyl acrylate hydrolysis product having a general formula (I): , (I) where a means an integer from 0 to 2, b means an integer from 1 to 3, and the sum a+b is from 1 to 3, R independently means non-branched or branched alkyl residue with 1 to 8 carbon atoms, cycloalkyl residue with 3 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6 to 10 carbon atoms in the aryl portion, R1 independently means hydrogen, non-branched or branched alkyl residue with 1 to 8 carbon atoms, cycloalkyl residue with 3 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6 to 10 carbon atoms in the aryl portion, R2 independently means hydrogen, non-branched or branched alkyl residue with 1 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6 to 10 carbon atoms, R3 means single bond, or non-branched or branched, if necessary, substituted alkylene residue (alkane dienyl residue) with 1 to 8 carbon atoms in alkylene residue, or, if necessary, substituted arylene residue (aryl dienyl residue) with 6 to 10 carbon atoms in arylene residue, (C) from 25 to 90% by mass of at least one acrylate monomer of general formula (II) where n means a number from 1 to 6, R4 means hydrogen, non-branched or branched alkyl residue with 1 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6 to 10 carbon atoms in the aryl portion and where substituents R4 may be the same or different; R5 means unsubstituted or substituted organic residue having a valency from 1 to 6 such as, if necessary, substituted, non-branched or branched aliphatic or aromatic hydrocarbon residue with 1 to 20 carbon atoms, and (D) from 0.01 to 15% by mass of at least one UV photoinitiator, respectively, with respect to the total mass of the composition, the composition being intended for coating transparent, polycarbonate-based, optical information carriers.

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3 cl, 2 tbl, 4 ex

FIELD: transportation.

SUBSTANCE: proposed coating includes a lower layer of an aluminum alloy anodic oxide coating and an upper layer representing a thermo regulating paint coat comprising acrylate holmium-containing vanish "АКГ-1,2" (42-38 percent by weight) and oxide-modified zirconium (IV), 7-4 (58-62 percent by weight). The coating features low solar radiation absorption factor values (As ≤ 0,10-0,11) and high radiation factors (ε≥0,92-0,94). This allows reducing the radiator-emitter area which is particularly important in development of promising spacecrafts. Availability of two thermoregulating coatings, i.e. the anodic oxide and paint coatings allows a notable increase in service life of the said radiators and producing the said coatings on the surface of products made from aluminum or its alloys with lower As/ε parameter values and without drawbacks inherent in silicate coatings.

EFFECT: antirust protection of complicated-design structures and provision of preset thermal-and-radiation characteristics.

2 tbl

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