Composition for application onto metal and concrete surfaces

FIELD: construction.

SUBSTANCE: invention represents an emulsion, in which oligomers with terminal isocyanate groups are a dispersion medium, and a disperse phase is a solution or a dispersion produced as a result of mixing a lime solution with calcium hydroxide content of 10-70 wt % with glycerine in the amount of 1-250 wt parts per 100 wt parts of calcium hydroxide, besides, the disperse phase content in the composition makes 1-55 wt %.

EFFECT: development of a cheap and easy to apply composition, coatings from which have high adhesion to moist metal or concrete surfaces, have proper adhesion to concrete applied onto them, are hardened with specified speed at temperature from zero and above, inhibit processes of metal corrosion and have low elasticity module.

1 tbl

 

The invention relates to compositions based on isocyanates used for coating on metal or concrete surfaces, especially for polymeric coatings on degraded surfaces of underground pipelines during their rehabilitation, as well as inhibition of primer when painting metal and as a sealant.

Often metal and concrete surfaces, which is necessary to apply a polymer coating, are not stationary in controlled factory conditions, and in conditions where they have long been exposed to the environment. In the latter case, these surface defects and contamination and, as a rule, are wet, so to compositions, which serves for drawing on such surfaces, the requirements are higher: they must have sufficient adhesion even to such defective damp surfaces.

In addition, if the polymer coating, the resulting coating composition is used as an intermediate layer for adhesion to old concrete or metal freshly applied concrete mix, it needs to provide high adhesion to it of deposited concrete, as a rule, the shotcrete.

Known curable composition according to patent RU 2259378, which is 100 wt.% unsaturated oligoester and cross-linking agents which contains 1-50 wt.% polybutadiene. The curing of this composition after application is carried out using ultraviolet light.

The composition for obtaining the polyurethane coating according to patent US 6291625 contains paleologou composition and the polyisocyanate. Palilula composition is obtained by mixing the triglyceride12-C25hydroxy-substituted fatty acid and calcium hydroxide for the hydrolysis of triglycerides and the formation of fatty acids in free form and glycerol followed by emiliania fatty acids for the formation of salts of fatty acids. Calcium hydroxide is taken in the amount of at least 0.1 mol per mole of triglyceride.

The composition according to EP 0145269 is a two-component system. The first component contains a water soluble or dispersible alkali, which reacts with carbon dioxide, emulsifying agent and at least one polyol having a primary hydroxyl group. The second component contains a prepolymer with terminal isocyanate groups dissolved in an organic solvent, additional polyisocyanate and carefully dried filler.

None of these compositions does not meet adequately the requirements specified above. In addition, none of these compositions do not provide the polymer coating, which can firmly stick to put on not what about the shotcrete.

The basis of the invention tasked to develop a composition that provides high adhesion of the obtained polymer coating with wet metal and concrete surfaces, which has a high adhesion to the applied polymeric coating to the concrete and which is inexpensive and easy to use.

In compositions for application to metal or concrete surfaces containing oligomers with terminal isocyanate groups and the calcium hydroxide, the problem is solved by the fact that it is an emulsion, in which the oligomers with terminal isocyanate groups are dispersion medium and the dispersed phase is a solution or dispersion obtained by mixing lime mortar containing calcium hydroxide 10-70 wt.%, and glycerol in the amount of about 1-250 moschata 100 moschata of peroxide calcium, and the content in the composition of the dispersed phase is 1-55 wt.%.

Preferably, as oligomers with terminal isocyanate groups it contains a diisocyanate selected from the group comprising polybutadiene and macrodiisocyanate, resulting from the interaction of the polyether with a diisocyanate, hexamethylenediisocyanate or diphenylmethanediisocyanate.

As oligomers with terminal isocyanate which groups the composition may contain triisocyanate on the basis of polypropilencolour.

The polymer composition is an emulsion, in which the dispersion medium are oligomers with terminal isocyanate groups of the diisocyanates (DITS), and the dispersed phase is a solution or dispersion of calcium hydroxide in water - mortar (IL) with the addition of glycerol. Two molecules of glycerol on the secondary hydroxyl groups can react with one molecule of calcium hydroxide with the formation of glycerate calcium - dogsleding calcium hydroxide. However, in accordance with the invention, the mass ratio of calcium hydroxide and glycerol, introduced in IL selected such that not all of the calcium hydroxide has turned into glycerin calcium. Thanks in IL along with a solution or dispersion in water glycerate calcium is the product of the interaction of one molecule of glycerol and one molecule of calcium hydroxide - one-deputizing calcium hydroxide (GGC).

Specialist clear that instead of calcium hydroxide in some cases can be used hydroxides other selectionne metals.

As DIEZ usually used the prepolymer Krasol LBD (Czech Republic) - polybutadiene with a content of NCO groups of 3.2% (PBDES) or macrodiisocyanate (prepolymers), resulting from the interaction of polyethers, for example, polypropylenglycol (BCP) or polytetramethylene (PTMG) with t larentiinae (TDI), hexamethylenediisocyanate (HMDI) or diphenylmethanediisocyanate (DFMGI). As oligomers can be used also triisocyanate based on, for example, polypropilencolour (ETF). Obtained on the basis of these products polymers are elastic, high strength and alkali. The elasticity and strength of polymers is easily regulated by changing the type of MDI and its molecular weight. In addition, the composition can be well-known substances used in the preparation of polyurethanes: plasticizers, Monomeric diisocyanates, glycols, triodes, catalysts, pigments, fillers, flame retardants and other

Curing DIEZ is mainly due to the interaction of isocyanate groups with water interphase released during this interaction, the carbon dioxide is rapidly absorbed by water and its calcium hydroxide, which excludes the possibility of foaming of the composition. The rate of interaction of isocyanate groups with water in an alkaline medium is relatively high, which complicates the practical use of the composition in hard to reach places, for example, when it is applied to the internal surface of pipelines. Reduce speed by reducing the concentration in the composition of the IL is not desirable, as this may cause foaming of the composition. Slimming the speed of this interaction and, therefore, increasing the viability of the composition can be easily achieved by the introduction of substances that do not react with isocyanate groups and focusing on the interphase boundary. As such substances can be used surfactants, bitumen or their solutions, polymer solutions, the waste chemical plants, etc.

Isocyanate groups react with the primary hydroxyl groups GGC. Molecules of product formed have pronounced defininetly, which explains the high adhesion of the polymer to wet the metal and wet concrete. In addition, it can be assumed that one-deputizing calcium hydroxide may participate in the hydration process of the concrete mix, ensuring high adhesion thereto of the resulting polymer.

Corrosion activity of the composition is determined by the presence in it of a solution of calcium hydroxide and GGC, and the solubility in water GGC several times higher than that of calcium hydroxide, which significantly increases the protective properties of the coating.

The composition has low cost, as it as diluent is water.

The table below shows examples of compositions that have been put to the test when applied to the surface of metal or concrete in various conditions. Compositions were prepared immediately before ispytaniyam mixing ingredients. Glycerol was introduced to the lime solution containing calcium hydroxide 40 wt.%, the rest is water. The ratio of oligomer: IL+glycerol in the composition was equal to 60:40. For the adhesion test composition with a thickness of 1 mm was applied to the surface of metal or concrete plates, after 1 hour, the composition was applied concrete thickness of 10 mm Blend made from Portland cement PC 11/B-sh-400, sand with fineness modulus of 1.5, the ratio of cement-sand was 1:3, water / cement ratio of 0.5, the Hardening of the concrete mixture was at room temperature. One month after spraying it with epoxy glue glued a metal mold and made his breakaway in the PosiTest adhesion meter, DeFelsko.

№ p/pComponents of the synthesis DIEZQuantity of glycerol in IL, %Material plateAdhesive strength, MPaThe destruction of nature
1TDI-Steel0,2Adhesive,
BCP-502 drypolymer -
the shotcrete
2TDI-Steel0,2Adhesive
BCP-502wetsteel-polymer
3TDI-Concrete0,2Adhesive
BCP-502wetpolymer -
the shotcrete
4TDI15 Steel2,8Cohesion
BCP-502wetthe shotcrete
5TDI-Steel0,1Adhesive
BCP-1002drypolymer -
the shotcrete
6TDI-Steel0,1Adhesive
BCP-1002wetsteel - polymer
7 TDI0,1Steel0,3Adhesive
BCP-1002wetsteel - polymer
8TDI0,5Steel0,9Adhesive
BCP-1002wetpolymer -
the shotcrete
9TDI1Steel1,6Adhesive
BCP-1002wetpolymer -
the shotcrete
10TDI5Steel2,6Cohesion
BCP-1002wetthe shotcrete
11TDI20Steel2,7Cohesion
BCP-1002wetthe shotcrete
12TDI50Steel2,7Cohesion
BCP-1002wet the shotcrete
13TDI70Steel1,6Adhesive
BCP-1002wetpolymer -
the shotcrete
14TDI80Steel0,7Adhesive
BCP-1002wetpolymer - steel
15TDI20Concrete2,6Cohesion
BCP-1002wetthe shotcrete
16TDI15Steel2,3Cohesion
BCP-2002wetthe polymer
17TDI15Steel2,8Cohesion
PTMG-902wetthe shotcrete
18PBDIT15Steel2,7Cohesion
wetthe polymer
19PBDIT-90% 15Steel2,9Cohesion
+TDI-10%weton tortureblow
20PBDIT15Concrete2,6Cohesion
wetthe polymer
21PBDIT-90%-Concrete0,2Adhesive
+TDI-10%wetpolymer-concrete
22DFMGI15Steel2,9Cohesion
BCP-1002wetthe shotcrete
23HMDI15Steel2,7Cohesion
BCP-502wetthe shotcrete
24TDI5Steel1,1Cohesion
PPT-5003wetthe polymer

The number after the name of the polyester denotes the molecular weight of the polyester, the last digit is its functionality.

As can be seen from the table, the composition does not contain glycerin, may not be used for rehabilitation of pipelines with concrete mix due to poor adhesion of the composition to wet the metal, wet is etono and shotcrete. Part No. 13, when the content in IL-70% glycerol, it is almost all spent on the education of glycerate calcium and, since this concentration, a sharp decrease of the adhesion strength of the polymer as to wet the metal and concrete. As can be seen from the table, the recommended content of glycerol in IL must lie in the range 1-70%. Thus, the main factor determining the adhesion strength is the presence in the composition GGK, type oligomer is almost irrelevant.

The maximum value in the composition IL, above which there is an inversion of the phases is in the range of 45-55%. The minimum value below which can cause foaming of the coating thickness of 1 mm at room temperature, is a composition based on TDI and BCP-502 35-40%, TDI and BCP-1002 30-35%, DFMGI-PTMG-902 - 15-20%, PBDES - 1-5%, HMDI and GPR-1002 10-15%.

The water content in the IL can vary from 10 to 99%, with extreme values of the absorption rate of carbon dioxide released during the interaction of the isocyanate groups with water is small, the recommended values 30-90%.

The thickness of the polymer coating on the inner surface of the pipeline depends on the surface condition of the metal, the diameter of the pipeline and the possible magnitude of deformation of the pipe due to soil movements and is in the range of 0.1-10 mm within these limits fizi what about the mechanical properties of the coating are almost unchanged. The change in temperature curing of the composition in the range 0-40°C also does not lead to significant changes in polymer properties.

The curing time of the composition depends on the composition of the oligomer and temperature. So, at 20°C curing time songs is: TDI and BCP-502 20-30 min, TDI and BCP-1002 30-40 min, DFMGI-PTMG 25-35 min, PBDES 3-4 hours, HMDI and GPR 1-2 hours. Changing the temperature of the curing composition 10°C leads to a change in the curing time is approximately 2 times. After curing of the composition of its ability to form a strong adhesive bond with shotcrete lasts for 1-3 days.

The cheapest and most technologically suitable is a composition based on TDI and BCP-1002, however, a high curing rate hinders its practical application. Due to the fact that the curing reaction of the composition occurs at the interface polymer - water, surface-active substances, which are concentrated on interphase dramatically reduces the rate of curing. As the surfactant, it is recommended to use well-known anion active (alkylarylsulfonate, alkylcyclohexanes, naphthalenesulfonate, salt perforated carboxylic acids and others) or non-ionic substances (e.g., block copolymers), which not only reduce the curing speed of the composition, but both is that the uniform nerastraivaisya patterns. Reduces curing rate of the composition an introduction to its water-repellent agent composition, for example solutions of bitumen or paraffins in the hydrocarbon. Thus, the introduction into the composition 10% of a one percent solution of bitumen in xylene reduces the rate of curing in 3-4 times, and perfluorinated carboxylic acids in 4-5 times.

Thus the coatings produced with the use of a composition according to the invention have the following properties:

1. Have good adhesion to metal or concrete, including wet surfaces.

2. Have good adhesion to put on them to shotcrete.

3. Otverzhdajutsja a given speed at a temperature between zero and above.

4. Inhibit the corrosion of metal.

5. Have a low modulus of elasticity.

1. Composition for application to metal or concrete surfaces containing oligomers with terminal isocyanate groups and calcium hydroxide, characterized in that it is an emulsion, in which the oligomers with terminal isocyanate groups are dispersion medium and the dispersed phase is a solution or dispersion obtained by mixing lime mortar containing calcium hydroxide 10-70 wt.% with glycerol in the amount of about 1-250 parts by weight per 100 parts by weight of peroxide calcium, and the content in the composition of the dispersed phase costal is no 1-55 wt.%.

2. The composition according to claim 1, characterized in that as oligomers with terminal isocyanate groups it contains a diisocyanate selected from the group comprising polybutadiene and macrodiisocyanate, resulting from the interaction of the polyether with a diisocyanate, hexamethylenediisocyanate or diphenylmethanediisocyanate.

3. The composition according to claim 1, characterized in that as oligomers with terminal isocyanate groups it contains triisocyanate on the basis of polypropilencolour.



 

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13 cl, 10 ex, 1 tbl

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13 cl, 6 ex, 4 tbl

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15 cl, 6 tbl

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14 cl, 2 tbl

FIELD: chemistry.

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9 cl, 6 ex, 5 tbl

FIELD: chemistry.

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5 cl, 3 tbl

FIELD: chemistry of polymers.

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11 cl, 5 tbl, 12 ex

FIELD: chemical industry; methods of production of a thermosetting elastomers.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of production of a thermosetting polyurethane elastomer and also to the elastomer produced according to the given method. The invention presents the method of production of the polyurethane elastomer having a total apparent density exceeding 150 kg/m3 and providing for an interaction of polyisocyanate and a reactive to isocyanate composition not necessarily at presence of water, according to which the reaction conduct at an isocyanate index of 85-120. At that the polyisocyanate component is composed of: al) 80-100 mass % of diphenylmethanediisocyanate containing at least 40 mass % of 4.4'- diphenylmethanediisocyanate and-or a derivative of the indicated diphenylmethanediisocyanate, which (the derivative) is a may be a liquid at the temperature of 25°C and has NCO value of no less than 20 mass % and a2) 20 mass % of the other polyisocyanate; the reactive to isocyanate composition b) consists of b1) 80-100 mass % of a simple polyol polyester having an average nominal functionality - 2-8, average reactive equivalent weight of 750-5000, an average molecular mass of 2000-12000, the share of oxyethylene - 60-90 mass % and the share of the primary hydroxyl groups of 70-100 mass % calculated for the total number of the primary and the secondary hydroxyl groups in polyol; b2) a reactive to isocyanate extender of the chain in such a quantity, that the ratio of the rigid block makes less than 0.45; and b3) - 20-0 mass % of one or more of other reactive to isocyanate composition excluding water. At that the amount of the polyol of 61) and the reactive to isocyanate composition 63) is calculated from the total amount of the indicated polyol 61) and the composition 63). The invention presents also description of the thermosetting elastomer produced according to the indicated method.

EFFECT: the invention ensures production of a thermosetting polyurethane elastomer.

10 cl, 2 ex

The invention relates to a light-resistant, elastomeric, polyurethane moulded products

FIELD: chemistry.

SUBSTANCE: invention relates to aldimines of formula (I)

where A does not contain active hydrogen and a primary amine group, or together with R7 denotes a (n+2)-valent hydrocarbon radical containing 3-20 carbon atoms and, if necessary, at least one heteroatom in form of oxygen of an ether group or nitrogen or a tertiary amine group; n equals 1, 2, 3 or 4; m equals 0,1, 2, 3 or 4; R1 and R2 each denotes a univalent hydrocarbon residue with 1-12 carbon atoms or together denote a divalent hydrocarbon radical which is part of a carbocyclic ring with 5-8 carbon atoms; R3 denotes H or alkyl; R4 and R5 independently denote CH3 or a univalent aliphatic radical containing 2-12 carbon atoms and optionally hydroxy groups; X denotes O, S, N-R6, or N-R7, where R6 denotes a univalent hydrocarbon radical containing 1-20 carbon atoms and having at least one hydroxy group; as well as curable compositions containing such aldimines and use of said compositions.

EFFECT: obtaining novel aldimines which can be used as curing agents in curable compositions.

22 cl, 18 ex, 6 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethane which contains a reaction product of components, containing: (a) a urethane prepolymer with isocyanate functionality containing a reaction product: (i) about 1 equivalent of at least one polyisocyanate; (ii) about 0.1 to about 0.5 equivalents of at least one diol having 2 to 18 carbon atoms; and (b) about 0.05 to about 0.9 equivalents of at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and (c) less than about 0.45 equivalents of at least one diol having 2 to 18 carbon atoms, wherein the reaction product of components contains less than about 5 wt % polyester polyol, polyether polyol and/or an amine curing agent. Described also are an article, a laminate and a coating composition containing such polyurethane.

EFFECT: production of polyurethanes, articles from which have good optical properties, high resistance to impact loads, high impact viscosity, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

25 cl, 110 ex, 33 tbl, 26 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a two-component adhesive for gluing wooden materials, as well as a method of producing said adhesive. Said adhesive contains an isocyanate-containing component A and an amine-containing component B. Component A contains a prepolymer with a terminal isocyanate group with isocyanate functionality ≥ 1.7, preferably 1.7<fNco<3, more preferably in the range of 2-3, and component B contains at least one diamine and/or polyamine, preferably a diamine polyether and/or a polyamine polyether. Stoichiometric ratio of isocyanate groups in component A to amine groups in component B is equal to 0.5-1.2, more preferably 1.

EFFECT: obtaining a two-component adhesive which ensures strength, stability and improved load-bearing capacity of the obtained bond, and also having improved light fastness.

10 cl, 3 ex

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