UA73564C2 - Polyurethane foamed materials with a low exothermy and a method for the preparation thereof - Google Patents

Abstract

The invention concerns polyurethane foams with reduced exothermy and to the use thereof for hardening rocks in mining and underground engineering.

Description

Description of the invention

The invention relates to polyurethane foam systems with low exotherm, as well as their use for 2 strengthening of geological rocks in the underground mining industry, tunnel construction, as well as in underground construction. In underground coal mining, two-component polyurethane foam systems are used in a large volume to strengthen rocks and coal , as well as for evaporation of groundwater.

The polyurethane component of polyisocyanates and polyols is mainly exothermic. Under adverse conditions, due to the high reaction temperature, ignition of coal dust may occur. Especially when the mixture 70 is fed into larger containers, the temperature of the polyurethane foam element can increase to such an extent that it can cause the polyurethane to self-ignite and, as a result, the coal to ignite.

In order to avoid this disadvantage of polyurethane systems, EP-A 167002 suggests using the products of the isocyanate exchange reaction with an aqueous alkyl silicate solution. EP-A 636154 deals with the exchange reaction of polyisocyanates, alkyl silicate solutions and cement. But these systems cannot be used in practice. It has been proven that with the help of a combination of isocyanate-prepolymer with selected polyols and appropriate fillers, the exotherm of the polyurethane component can be reduced so much that when the rocks harden there is no longer a risk of fire.

Therefore, the object of the invention is foam components containing polyurethane groups, obtained as a result of the exchange reaction of a) polyisocyanate component with an MSO content of 20-3Omas.9o, preferably 23-28oMas.95, which contains at least 5Omas.9o prepolymer, which includes isocyanate groups, with an MSO content of 20-28 wt.oo, b) a polyol component with an amount of OH of 120-350, preferably 180-300,8) dispersed in the polyol component b) or in the prepolymer a) a solid filler with an average particle size of 4- 100 µm, preferably 4-25 µm, in particular 10-25 µm, c 29 g) water, He) e) if catalysts are needed, f) if additional additives are needed.

According to the invention, the isocyanate component contains 20-3Omas.95, preferably 23-28wt.bo MCO groups and at least 5Omas.bo prepolymer, which includes 20-3Omas.9o, preferably 23-28wt.oo, isocyanate M groups. This prepolymer is obtained mainly by the reaction of exchange of isocyanates of the diphenylmethane series with He) polyether polyols with a functionality of 3-8 and with an amount of OH of 350-1000, as well as an average molecular weight of 150-1000. Corresponding prepolymers are also described in the European patent EP-A 550901. As isocyanates of the diphenylmethane series, diatomic diphenylmethane isocyanates are used, such as 4,4- and/or co 2,4-diphenylmethane isocyanate, or their homologues, or, accordingly, mixtures of di- or polyatomic 325 diphenylmethane isocyanates, for example, polyphenylene polymethylene polyisocyanates, obtained by - aniline-formaldehyde condensation and final phosgenation ("crude MDI"), or polycyanates called "polymeric diphenylmethane diisocyanate", which are obtained by a technical method, with a higher functionality than 2.0.

Preference is given to products containing 75-95% by weight of diatomic isomers, in particular those in which the content of the 2,4-isomer in diatomic isomers is 15-4% by weight, and the content of the 2,2-isomer is 2-1% by weight. - 50 Along with the prepolymer, the isocyanate component a) may contain up to 5% by mass of other isocyanates of the diphenylmethane series. Therefore, polymer MDI is preferred. But it can also be used here

From" monomeric MDI, or, for example, modified types of MDI containing biuret, allophanate or isocyanurate groups, until the viscosity of the isocyanate component a) is increased in this way. In order to ensure proper processing of the isocyanate component a), its predominant viscosity is achieved 200-6000mPas, especially 500-3000mPas. Such isocyanate components are best pumped with piston and gear pumps, which are commonly used for rock strengthening, and injected into the rock. The polyol component b) contains a certain amount of OH groups 120-350, preferably 180-300. Preference is given to such polyol components as polyoxyalkylene polyols with a functionality of 2-8, preferably 2-4, obtained as a result of the polymerization of alkylene oxides, such as, for example, ethylene oxide, propylene oxide, butylene oxide,

Gee! 20 decyloxirane or phenyloxirane, preferably ethylene oxide and/or propylene oxide, with compounds containing active carbon atoms. First, compounds with two or more hydroxyl groups are used, such as, for example, water, triethanolamine, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,2 -butanediol, 1,3-butanediol, /1,4-butanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6b-hexanediol, glycerin, trimethylolpropane, 29 pentaerythritol or sorbitol. These parent compounds can be used either alone or as mixtures.

GF) The composition of the polyol component b) may also include one or more polyester polyols in the amount of up to 1 Omas.bo from the total amount of the component b). Suitable polyester polyols have an average molecular weight of 200-6000 g/mol, preferably 200-2400 g/mol, and are obtained from aromatic and/or aliphatic dicarboxylic acids and polyols containing at least two hydroxyl groups. Examples of dicarboxylic acids include 60 phthalic, isophthalic, terephthalic, fumaric, maleic, azelaic, glutaric, adipic, coric, sebacic, malonic and succinic acids. Both pure dicarboxylic acids and any of their mixtures can be used. Instead of free dicarboxylic acids, suitable derivatives of dicarboxylic acids can also be used, such as, for example, dicarboxylic mono- or diester alcohols with 1-4 carbon atoms. Such esters are obtained, for example, during the processing of polyester waste. Dicarboxylic acid anhydrides, such as phthalic or maleic anhydride, can also be used as acid components. Ethylene glycol, diethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerin are mainly used as alcohol components for hardening. , trimethylolpropane, pentaerythritol or, accordingly, their mixtures. Polyester polyols from lactones, such as ε-caprolactone, or hydroxycarboxylic acids, such as o-hydroxycarboxylic acids, can also be used. The polyol component can also contain polyetherester polyols obtained, for example, as a result of the reaction of phthalic anhydride and diethylene glycol, as well as the subsequent exchange reaction with oxirane. When manufacturing foamed materials according to the invention, a solid filler with an average particle size of 4-100 μm is used as component c) , mostly 4-25μm, in particular 70. 10-25μm. Such fillers make it possible to obtain dispersions with the necessary viscosity for processing. Such fillers are, for example, aluminum trihydroxide, formaldehyde-urea resins (condensation products of urea and formaldehyde, see Notsrep-UUeu!, "Meiiodep deg ogdapizspep Spetier" | Houben-Weil "Methods of organic chemistry"), volume KHIM, 1963, p. .319-402), rock dust or pyrogenic silicic acid; aluminum trihydroxide is preferred. For the production of foamed materials according to the invention, the solid 75 filler is dispersed or, accordingly, suspended in the polyol component b) or in the prepolymer a), preferably in the polyol component b). The filler mainly contains 30-55% by weight, in particular 35-5% by weight.

If the filler is dispersed in the polyol component b), then the viscosity of the polyol component should preferably be no more than bb0OmPas, so that it can be pumped with a low-pressure pump. The viscosity of the isocyanate and polyol components preferably have almost the same values to facilitate processing, in particular uniform mixing of the components.

For the production of foamed materials according to the invention, as a foaming agent d) water is used, preferably in the amount of 0.1 to 9% by weight, especially 0.6-0.9% by weight, depending on the polyol component b). In particular, the amount of water is determined in such a way as to achieve a foaming index of 2-6, i.e. so that the volume of the produced foam is one-sixth of the total volume of the final product. In the production of foamed materials according to the present invention, if necessary, catalysts e) can also be used, which accelerate the reaction between isocyanate and polyol components. Such catalysts are, for example, organic tin compounds, such as salts of tin (II) and organic carboxylic acids, such as tin (II) acetate, tin (II) octate, tin (II) ethylhexoate and tin (II) laurate, and dialkyl tin salts (IM), such as dibutyltin diacetate, dibutyltin dilaurate, and dioctyltin diacetate. The following examples of such catalysts are amines, for example, dimethylaminopropyl urea, dimethylaminopropylamine, bis-(dimethylaminopropyl)amine, diazabicyclooctane, dimethylethanolamine, triethylamine, dimethylcyclohexylamine, dimethylbenzylamine, pentamethyldiethylenetriamine,

M,M,M',M'-tetramethylbutanediamine, M-methylmorpholine, bis--(dimethylaminoethyl)ethertatris-(dialkylaminoalkyl)-z-hexahydrotriazine.

Catalysts for obtaining polyisocyanurate structures are, for example, potassium salts such as acetate or o

ZZ5 potassium octat. Combinations of several catalysts can also be used. h-

For the production of foamed materials according to the invention, if necessary, additives can also be used, for example, pigments, dyes or softeners, such as dioctyl phthalate. They are mostly added to the polyol component in the amount of O-TO mass particles, preferably 0-5 mass particles. "

If necessary, flame retardants are also added, preferably liquid and/or those that dissolve in one or more components used to make foamed materials. - c Commercially available flame retardants containing fluorine, for example, tricresyl phosphate, tris-(2-chloropropyl) phosphate, tris-(2,3-dibromopropyl) phosphate, tris-(1,3-dichloropropyl) phosphate, are mainly used phosphate, "» tetrakis-(2-chloroethyl)ethylene diphosphate, diethylethane phosphate, diethyl ester of diethanolaminomethylphosphoric acid. Polyols that protect against fire containing halogen or fluorine can also be used here. Flame retardants are used mainly in the amount of a maximum of 35wt.9o, especially - And a maximum of 2Omas.9o, depending on the component b). The object of the invention is also the use of foamed materials according to the invention for the solidification of rocks in the mining industry, in underground construction, o for example, for securing coal and side rocks, as well as for evaporation of groundwater in the underground coal industry.

In geologically dangerous zones, rocks are increasingly collapsing from the hanging side of the rock formation

Ф rocks, which significantly damages production and causes significant damage to a person working underground. "from" When strengthening rocks, polyurethane foam materials according to the invention are pumped through boreholes with the help of a suitable pump into the rock that needs to be strengthened. The reaction mixture seals the gaps and cracks and thus leads to the restoration of a strong connection of the rock; such

THEREFORE, the danger of rock or coal collapse is completely eliminated.

Foamed materials according to the invention are made preferably in such a way that the isocyanate component a) o and the mixture containing components b), c), d), e) and g) were mixed in a volume ratio of 1:11. At the same time, the MCO/OH ratio is preferably 130-300, especially 190-260.

The method of manufacturing foamed materials is chosen in such a way that the temperature reached by the reaction mixture does not exceed 1202C. Particular preference is given to methods in which the maximum reaction temperature does not exceed 11090.

Examples

In the examples below, the following source components were used:

Composition A: 65 Polyol mixture with an amount of OH of 239 mg of KOH/g, consisting of: 1) 20.09 wt.h. polyether with the amount of OH 190, obtained as a result of the reaction of exchange of propylene glycol with ethylene oxide, 2) 7 by mass part. polyether with an amount of ОН of 25 Омг KOH/g, obtained as a result of the exchange reaction of trimethylolpropane with ethylene oxide and propylene oxide,

Z) 0, Omas.ch. water as a foaming agent and 4) 0.2 wt.h. dibutyltin dilaurate as a catalyst.

Composition B:

A polyol mixture with an amount of OH of 111mg KOH/g, consisting of: 1) 98.O9wt.h. polyether with an amount of ОН 112, obtained as a result of the reaction of exchange of propylene glycol with 7/0 propylene oxide, 2) O, Umass.ch. of water as a foaming agent and 3) 0.2 wt.h. dibutyltin dilaurate as a catalyst.

Composition B:

A polyol mixture with an amount of ОН of 381 mg of KOH/g, consisting of: 1) 98.О9wt.h. of polyether with the amount of ОН 385, obtained as a result of the exchange reaction of trimethylolpropane with propylene oxide, 2) O,Umas.ch. of water as a foaming agent and 3) 0.2 parts by mass. dibutyltin dilaurate as a catalyst.

The composition of G.

A polyol mixture with an amount of OH of 242 mg of KOH/g, consisting of: 1) 98.9 wt.h. polyether with the amount of OH 245, obtained as a result of the exchange reaction of glycerol with propylene oxide, 2) O, Umass.ch. of water as a foaming agent and 3) 0.2 parts by mass. dibutyltin dilaurate as a catalyst.

Isocyanate | high school

Isocyanate prepolymer with an amount of МСО 25, bmas.b5 (OeztodigO MR.RO 28Н507, Bayer AG, 0-51368

Leverkusen); the product of polyisocyanate exchange, containing bOmas.9o of 4,4'-diisocyanate diphenylmethane and 22ws.9o i) of 2,4-diisocyanate diphenylmethane and Zmas.9o of 2,2'-diisocyanate diphenylmethane, with polyether polyol with the amount of ОН 865, which was obtained as a result of the reaction exchange of trimethylolpropane and propylene oxide, in the ratio of 92.5 wt.bo MDI/7.5 wt.bo polyol. « from Isocyanate II

Polyisocyanate with an amount of МСО 31mas.bo (Jueztodighe 4470 I, Bayer AG, 0-51368 Leverkusen), which is approximately ix, per Z'mas.b5, consists of diisocyanate diphenylmethane isomers, of which approximately 8Um.95 is 4,4-diisocyanate diphenylmethane, and approximately 11 wt.9b - 2,4"-diisocyanate diphenylmethane.

Aluminum hydroxide with an average particle size of 15-25 μm (Mapipaku me) OM-320, Martinswerk GmbH, 0-50127, Bergheim) was used as a filler. Cha

These components were tested in the laboratory in a known way: approximately 200 grams of components at a volume ratio of isocyanate to polyol of 1:11 were mixed at a raw material temperature of 232C. Then the reaction temperature in the middle of the experimental container was measured. After about 4 hours, the experimental container was cut and the structure of the foamed material was evaluated. "

The results of the experiment are presented in Table 1.

And" 111111opilad////////// || 45

Ameech! 77777771 185-11-75 pos vv vv - Bimechi 11111055 111

Vme 11111111 65111 about swords 11111111 1158-11 1 t 5o mani 77777111 new vo vo vo vo) av o mem! 11111111 110 s rvorav

І» dozi 00000006 5 yav yav yav yav, o Mecolial temperature such GO 000705, vv (1105 v 2 v7 55, ;

A: acceptable, K: collapse

Claims (5)

The formula of the invention 1. Foamed materials containing polyurethane groups, obtained as a result of the interaction reaction: 65 a) of a polyisocyanate component with an MSO content of 20-30 wt. 20-28 wt.9o, b) polyol component with an amount of ОН 120-350, c) dispersed in the polyol component b) or in the prepolymer a) solid filler with an average particle size of 4-100 μm, d) water, e) catalysts. 2. Foamed materials according to claim 1, which differ in that they contain additional additives e). C. Foamed materials according to claim 1 or 2, which are distinguished by the fact that they are suitable for fixing rocks in 70 the mining industry and underground construction. 4. The method of obtaining foamed materials containing polyurethane groups according to claim 1, in which the isocyanate component a) enters into an interaction reaction with a mixture containing components b), c), d) and e) in a volume ratio of 1 :1. 5. The method of obtaining foamed materials according to claim 4, which differs in that additional additives e) are introduced into the mixture of components b), c), d) cv and e). Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2005, M 8, 15.08.2005. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. 6) « (Se) IS) (ze) m. - with . and? -I (95) 1 Fo s» ime) 60 b5