Method of obtaining polyester polyols with small amount of dioxane wastes

FIELD: chemistry.

SUBSTANCE: claimed invention relates to obtaining and application of polyester polyols. described is method of obtaining polyester polyols, in which : at stage a) mixed are at least, one anhydride of carboxylic acid (A), selected from group, consisting of phthalic anhydride, trimellitic acid anhydride and pyrromellitic acid anhydride, and diethyleneglycol (B), and subjected to interaction, with molar ratio of components (B) to (A) being within the range from 1.5:1.0 to 0.7:1.0; total content of components (A) and (B) counted per the weight of all mixture components is within the range from 66 to 90 wt %, and at stage b) diethyleneglycol (B) is added to polyester polyol from stage a), with polyester polyol from stage a) has higher molecular weight than polyester polyol from stage b), polyester polyol from stage a) has molecular weight in the range 1400 and 430 g/mol and hydroxyl number in the range between 80 and 260 mg KOH/kg, polyester polyol from stage b) has molecular weight in the range 750 and 350 g/mol and hydroxyl number in the range between 150 and 320 mg KOH/kg, and at stage a) added is, at least, one other glycol (C) with 2-4 carbon atoms except diethyleneglycol and, at least, one aliphatic dicarboxylic acid (D) with 5-12 carbon atoms, and number of components (C) and (D) at stage a) is selected such that quantity of components (A), (B), (C) and (D) in mixture constitutes 100 wt %. Also described is method of obtaining foam polyurethane (PUR) or foam polyisocyanurate (PIR) styrofoams, including stages: a) interaction of polyester polyol, obtained by claimed method, with b) polyisocyanate-containing component, c) foaming agent, d) one or several catalysts, e) if necessary, with fire retardant and/or other auxiliary substances and additives. Described is application of foam polyurethanes (PUR) or foam polyisocyanurates (PIR), obtained by said method for obtaining metal-containing laminated composite materials. Described is metal-containing laminated composite element, including metal layer and layer, containing PUR- or PIR-styrofoam, obtained by method described above.

EFFECT: reduction of quantity of formed dioxane relative to quantity of used diethyleneglycol, in the process of obtaining polyester polyols.

9 cl, 5 tbl, 18 ex

The present invention relates to the production and application of complex polyether polyols synthesized, of at least one carboxylic acid anhydride and diethylene glycol, and the special of the reaction is significantly inhibited the formation of 1,4-dioxane from diethylene glycol.

Complex polyether polyols are an important component of many foam and no foam polyurethane systems. Used for the formation of polyurethanes complex polyether polyols contain the vast number of hydroxyl groups capable of further reaction with isocyanate groups. Molecular weight of ester of polyether polyols is typically in the range 200-5000 daltons. Obtaining them carried out, mainly, by polycondensation of polycarboxylic acids, especially dicarboxylic acids and polyols, especially diols, making carboxyl and hydroxyl groups in the conditions of dehydration react with the formation of ester groups. Alternatively, you can also use the anhydrides of polycarboxylic acids, for example phthalic anhydride.

Conditions of dehydration can be achieved, for example, degassing, removing the reaction water stream of inert gas or by azeotropic distillation with a separating agent (Houben-Weyl, Methods der organischen Chemie, Band 14/2, Makromolekulare Stoffe, Thieme Verlag Stutgart,Hrsg. E.Müller. S.1-47, 1963).

Specialist it is known that the esterification of the diethylene glycol aromatic phthalic acid, used mainly in the form of phthalic anhydride, as a by-product is undesirable 1,4-dioxane. Formed dioxane in obtaining in industrial plants is transferred together with the reaction water, and so it must be subjected to decomposition, for example, in a water treatment facility or should be burned after concentration. Because of these additional stages of the method increases the cost of production of complex polyetherpolyols as the target product.

Formed as a by-product of 1,4-dioxane leads to the fact that decreases the yield of the target product, as part of the used diethylene glycol is not introduced in the described complex polyetherpolyols, and, as described, is removed in the form of 1,4-dioxane from the reaction mixture. Therefore, the formation of 1,4-dioxane causes serious economic losses.

In addition, the amount of 1,4-dioxane, which can be obtained in industrial installations, limited set of allowed values. Therefore, limiting the number of dioxane leads in this case to limit the capacity to produce complex polyether polyols.

Therefore, the present invention is the reating a method of producing a complex of polyether polyols at least one anhydride of carboxylic acid and diethylene glycol, does not possess the disadvantages of the known prior art.

The present invention upon receipt of a complex of polyether polyols and at least one carboxylic acid anhydride and diethylene glycol is particularly limiting the number formed of dioxane relative to the amount of diethylene glycol. The number of dioxane may be limited to a value less than 7 g, preferably less than 5 g per 1 kg of used diethylene glycol.

Another objective of the present invention is to limit the number of generated dioxane in obtaining complex polyether polyols and at least one carboxylic acid anhydride and diethylene glycol in relation to the amount of diethylene glycol. The number of dioxane may be limited to a value less than 4 g per 1 kg of the formed complex polyetherpolyols, preferably less than 3 g per 1 kg

The aforementioned task is solved by a method of obtaining complex polyether polyols, and on stage:

a) mixing at least one carboxylic acid anhydride (a) and diethylene glycol (C) and subject to their interaction,

moreover, the molar ratio of components (B) to (A) is in the range from 1.5:1.0 to 0.7:1.0, and the weight percent is of componentof (a) and (b) in calculating the masses of all components of the mixture is in the range from 66 to 90 wt.%,

and on stage

b) to complex politically from the stage and add diethylene glycol (B)

polyetherpolyols from stage a) has a higher molecular weight than polyetherpolyols from stage b),

characterized in that in stage (a) add at least one other glycol (S) with 2-4 carbon atoms with the exception of diethylene glycol and at least one aliphatic dicarboxylic acid (D) with 5-12 carbon atoms or at least one glycol (E) with 5-10 carbon atoms and at least one dicarboxylic acid (F) to 4 carbon atoms.

The number of components (C), (D), (E) and (F) in stage a) is chosen so that the number of all components (A), (B), (C) and (D) or (E) and (F) in the mixture was 100 wt.%.

In a preferred embodiment of the invention, the carboxylic acid anhydride (A) is aromatic.

The carboxylic acid anhydride (A), preferably selected from the group consisting of phthalic anhydride, anhydride trimellitic acid and anhydride pyromellitic acid. Particularly preferred carboxylic acid anhydride is phthalic anhydride.

By replacing a small amount of aromatic dicarboxylic acid in an equivalent amount of aliphatic dicarboxylic acid (D) or (F) and by replacing a small amount diethylenglycol the La on an equivalent amount of glycols (C) or (E) the number of educated dioxane in obtaining complex polyether polyols are reduced significantly more until the desired degree, than as a result of dilution effect. The properties of the obtained polyether polyols remain almost identical, that is obtained by the method according to the invention the polyether polyols have the same properties as the corresponding polyether polyols obtained without the addition of aliphatic dicarboxylic acids (D) or (F) without the addition of glycols (C) or (E).

The glycol (S) with 2-4 carbon atoms, preferably selected from the group consisting of ethylene glycol, 1,3-propane diol, 2-methyl-1,3-propane diol, 1,2-propane diol. Particularly preferred glycol (S) with 2-4 carbon atoms is ethylene glycol.

Aliphatic dicarboxylic acid (D) with 5-12 carbon atoms, preferably selected from the group consisting of glutaric acid, adipic acid, pipelinewall acid, cork acid, azelaic acid, sabatinovka acid, undecadienal acid and dodecadienol acid. Particularly preferred dicarboxylic acids (D) with 5-12 carbon atoms are adipic acid or sabotinova acid.

Glycol (E) with 5-10 carbon atoms, preferably selected from the group consisting of 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexandiol and 1.8-octandiol. Particularly preferred glycol (E) with 5-10 carbon atoms is 3-methyl-1,5-pentanediol or 1,6-hexanediol.

Dicarboxylic Ki the lot (F) to 4 carbon atoms, preferably, selected from the group consisting of succinic acid, fumaric acid and maleic acid. Particularly preferred dicarboxylic acid (F) to 4 carbon atoms is succinic acid.

Dosing of diethylene glycol (C) in stage b), and bringing complex polyester to equilibrium operate so that the distribution of individual oligomers complex polyether polyols would be consistent with the distribution function of oligomers Flory (.J. Flory, Principles of Polymer-Chemistry, Cornell University Press, Ithaca, 1953, page 317 and fortfolgende). In equilibrium Flory complex polyether polyols previously named species always have the same distribution of oligomers and therefore cause constant material properties in respect of them made of polyurethane materials.

Dosing of diethylene glycol (C) in stage b) is carried out at any temperature as an intermediate product of stage a), and also added diethylene glycol. Added diethylene glycol preferably has a temperature of from room temperature to 60°C, and the intermediate product from step a) has a high temperature from 120 to 200°C. Diethylene glycol (B) add under laboratory conditions in a countercurrent of nitrogen, and in an industrial environment, preferably, by creating in the boiler vacuum. The number of added diethylene glycol (B) determine pore the STV hydroxyl number of the product from step a) and the hydroxyl number of the destination of the final product, and is also the largest source of the mixture by the following formula (I):

$$d\mathrm{about}b\mathrm{and}\mathrm{in}K\mathrm{and}d\mathrm{and}et\mathrm{and}lengl\mathrm{and}K\mathrm{about}lI\left(B\right)\mathrm{in}gp\mathrm{and}mm\mathrm{and}x=\left(Z-Y\right)\cdot M/\left(1053-Z\right)\left(I\right)$$

in which

Z corresponds to the target hydroxyl number in stage b),

Y corresponds found a hydroxyl number of from stage a),

M corresponds to the number of complex polyetherpolyols from the stage and the value 1053 corresponds to a hydroxyl number of diethylene glycol.

Adding diethylene glycol (b) may be carried out over a long period of time, for example from 1 to 5 hours continuously, evenly or unevenly, or instantly.

The molar ratio of (B) to (A)preferably is in the range from 1.2:1.0 to 0.75 to 1.0 second.

The molecular mass obtained in stage a) complex polyetherpolyols with terminal hydroxyl groups is a value ranging between 1400 and 430 g/m is al, particularly preferably, between 1120 and 490 g/mol.

Hydroxyl number obtained in stage a) complex polyetherpolyols is in the range between 80 and 260 mg KOH/kg, preferably between 100 and 230 mg KOH/kg While the hydroxyl number or molecular weight polyetherpolyols from stage a) are always dependent on the properties of the original substances at the stage of (a) theoretical hydroxyl number or theoretical molecular weight, which is based on the premise that dioxane is not formed, and the free Monomeric low molecular weight glycol is made from the reaction of the original part.

The molecular mass obtained in stage b) complex polyetherpolyols preferably is in the range between 750 and 350 g/mol, particularly preferably in the range between 620 and 370 g/mol.

Hydroxyl number obtained in stage b) complex polyester-polyol is preferably in the range between 150 and 320 g KOH/kg, more preferably between 180-300 g KOH/kg

The hydroxyl number is determined by the interaction of hydroxyl groups in the sample of the sample complex polyetherpolyols first with some excess anhydride, for example acetic anhydride, the hydrolysis of the excess anhydride and the determination of the content of free carboxyl groups by direct titration of a strong OS is a Finance, for example with sodium hydroxide. The difference between the amount introduced into the reaction in the form of carboxylic anhydride groups and experimentally found by the number of carboxyl groups is a measure of the content of hydroxyl groups in the sample the test sample. Since this figure is adjusted with the amount contained in the original sample sample carboxyl groups due to not quite complete esterification, i.e. the acid number and get a hydroxyl number. When this is carried out most often by sodium hydroxide titration is calculated on an equivalent amount of potassium hydroxide, resulting in the acid and hydroxyl numbers have a dimension in g KOH/kg between a hydroxyl number (#IT) and srednetsenovoj molecular weight (M) there is the following mathematical relationship:

M=(56100·F)/OH#

while F means srednecenovogo functionality (functionality related to the content of hydroxyl groups in the molecule, and is called a hydroxyl functionality). Usually hydroxyl functionality can be calculated by the formula produce complex polyetherpolyols.

Viscosity at 50°C obtained in stage b) complex polyetherpolyols is a value ranging between 400 and 3000 MPa·s, preferably between 450 and 1500 MPa is C.

The viscosity is determined by a cone-plate viscometer, for example Kegel-Platte-Viskosimeter Physica MCR 51 der Fa. Anton Paar, and extrapolate to zero shear rate. The polyols according to the invention are largely restructure-viscous.

The weight percent of components (a) and (b) in calculating the masses of all components, preferably, is between 66 and 90 wt.%, particularly preferably, in the range between 70 and 85 wt.%.

Obtained in stage b) complex polyether polyols have an acid number in the range from 0.5 to 3.5 mg KOH/g

The functionality F obtained in stage b) complex polyether polyols is preferably in the range from 1.9 to 3. The functionality of more than 2 is obtained due to the fact that when the esterification of partially share the structural links with the functionality of more than 2, for example trioli or tetraol, and/or three - or tetracarbonyl acid and/or trifunctional hydroxycarbonate acid. Typical representatives are glycerol, 1,1,1-trimethylolpropane, pentaerythritol, trimellitate acid, tremezzina acid, malic acid, tartaric acid, citric acid, dimethylolpropionic acid, etc. Functionality F in the range from 2.0 to 2.3, preferably, can be achieved by using glycerol or 1,1,1-trimethylolpropane. At this viscosity, u is fair at 25°C, differs by less than 20 per cent of the viscosity measured for functionality and hydroxyl number of the same complex polyetherpolyols synthesized along with increasing the functionality of the component (for example, 1,1,1-trimethylolpropane) exclusively from phthalic anhydride and diethylene glycol.

To obtain complex polyether polyols according to the invention, preferably, use a vacuum at a pressure ranging from normal pressure to 5 mbar final vacuum, preferably up to 10 mbar final vacuum and temperature in the range of 100-230°C, preferably from 180 to 215°C.

The method of obtaining complex polyether polyols according to the invention is preferably carried out while applying all components of stage a) and subsequent condensation of their first at atmospheric pressure in the presence of a protective gas at a temperature of from 100 to 230°C., particularly preferably at a temperature in the range from 180 to 215°C to lack of reaction water in the process of distillation, distillation, and then, if necessary, after adding the catalyst for the esterification of the pressure decrease within 1 to 4 hours to below 20 mbar and the final polycondensation at a temperature in the range from 180 to 215°C. and full vacuum the flow of water until an acid number of 5 g KOH/kg

To obtain a complex of polyether polyols and the finding can be used all known specialist catalysts. Preferably, use chloride of divalent zinc and Tetra-alkoxylate titanium.

The interaction of components to produce complex polyether polyols according to the invention is preferably carried out in the mass.

Alternatively, complex polyether polyols can be obtained by way of purging with nitrogen, in which the condensate is taken out from the reaction vessel by a stream of nitrogen (J.H. Saunders und H..Frisch in Polyurethanes: Chemistry and Technology, Part I. Chemistry, Interscience published by John Wiley and Sons, New York 1962, page 45).

Another object of the present invention is a method for polyurethane-polyisocyanurate (PUR-PIR, PUR-PIR) foam, which includes stages:

a) interaction of complex polyetherpolyols obtained as described above, with

b) polyisocyanates component

c) a blowing agent,

d) one or more catalysts,

e) optionally, a flame retardant and/or other auxiliary substances and additives.

Polyisocyanurate component includes polyisocyanates.

Used polyisocyanates are usually used in the field of polyurethanes by the isocyanate. Usually use aliphatic, cycloaliphatic, aromatic and aromatic multifunctional isocyanate. It is preferable to use aromatic di - and polyisocyanates. A preferred example of JW is Auda 2,4 - and 2,6-toluylenediisocyanate, as well as any mixtures of these isomers, 2,2'-, 2,4'- and 4,4'-diphenylmethanediisocyanate, as well as any mixtures of these isomers, mixtures of 2,2'-, 2,4'- and 4,4'-diphenylmethanediisocyanate (dual - MDI) and polyvinylpolypyrrolidone (MDI). The alternative may also be used mixtures of toluylenediisocyanate and MDI.

As the foaming means can be used known compounds with the chemical and physical action. As a chemically acting blowing means can preferably be used in water. Examples of the physical foaming funds are cycloaliphatic hydrocarbons with 4 to 8 carbon atoms, such as HFC and HFCKW, which evaporate under the conditions of formation of polyurethane. In a preferred embodiment, the method as a foaming tools use pentane and cyclopentane, and mixtures of pentane and cyclopentane.

The number of used foaming tool depends mainly on the desired density of the foam. Water is most commonly used in quantities of from 0 to 5 wt.% of the total composition, preferably from 0.1 to 3 wt.%. In the General case, physically acting blowing means may be used in amounts of from 0 to 8 wt.%, preferably, from 0.1 to 5 wt.%. As the foaming means can also be used with carbon dioxide, which solution is between source components, preferably, in the form of a gas.

As catalysts for polyurethane or polyisocyanurate foams using conventional and well-known catalysts for the formation of polyurethanes or polyisocyanurates, for example organic tin compounds such as tin diacetate, diktat tin, dibutyltindilaurate, and/or strongly basic amines, such as 2,2,2-diazabicyclo, triethylamine or preferably, triethylenediamine or bis(N,N-dimethylaminoethyl) ether, as well as for catalysis PIR reaction, potassium acetate and aliphatic Quaternary ammonium salt.

The catalysts preferably used in quantities of from 0.1 to 3 wt.%, preferably, from 0.5 to 2 wt.% calculated on the total weight of all components.

The interaction of the above components, if necessary, is carried out in the presence of auxiliary substances and/or additives, such as regulators porosity, insulating means, pigments, reinforcing substances (amps), such as glass fibers, surfactants and/or stabilizers, oxidative, thermal, hydrolytic, microbiological degradation or aging. Polyurethane foams typically have a density of from 20 to 250 g/l, preferably from 25 to 150 g/l, particularly preferably from 30 to 100 g/l, most preferably from 35 to 5 g/L.

To obtain polyurethane foams according to the invention, as a rule, mix all of the components commonly used in the mixing head, operating at elevated or reduced pressure, in a quantity sufficient for their interaction in an equivalent ratio of isocyanate NCO groups to the sum of reactive hydrogen atoms, which in the case of PUR-foam is in the range of 0.80:1.00 and up to 1.60:1.00 and, preferably, between about 0.90:1.00 to 1,15:1,00. The ratio of 1.00:1.00 and corresponds to NCO index of 100.

In the case of PUR/PIR foam (PUR/PIR) is equivalent to the ratio of the amount of NCO groups to reactive to hydrogen atoms is in the range of 1.60:1.00 to 5.00:1.00 and, preferably, between 2,00:of 1.00 to 4.00:1.00 each.

Another object of the present invention is the use of complex polyether polyols obtained by the method described above, to obtain polyurethanes. Polyurethanes are material multilateral mission, which is used in many areas. Due to the diversity of the original substance can be derived products with different properties, such as rigid foams for insulation, block soft foams for mattresses, molded soft foam for car seats and cushions for seats, acoustic foams for insulation, thermoplastic foam is, foams for shoes or microporous foams, as well as compact injection system and thermoplastic polyurethanes.

The next object of the present invention is the use of PUR/PIR foams obtained as described above, to obtain a metal-containing layered composite elements.

Metal-containing layered composite elements are sandwich-layered composite elements consisting of at least two coating layers and located between the layer of the kernel. Preferably, the metal-containing layered foam composite elements composed of at least two coating layers of the metal layer and a core of foam plastic, such as rigid polyurethane (PUR) foam or polyurethane/polyisocyanurate (PUR/PIR) rigid foam. Such a layered composite elements of metal and foam long been known from the prior art and are also called metal-containing layered composite elements. Between the layer of core and coating layers may be provided with other layers. For example, the coating layers can be covered with a varnish.

Examples of the use of such metal-containing layered composite elements are flat and lirovannye details of the walls and profiled parts roofs for industrial building is listwa and production of refrigerators, and for LKW-production of doors for garages or containers for transportation.

These metal-containing layered composite elements may be continuous or periodic manner. Device for continuous get them known, for example, from German patent application DE 1609668 AND or DE 1247612 A.

In another embodiment of the method according to the invention in the polyol as one component A) complex polyetherpolyols A1) is contained in an amount of ≥60 to ≤70 wt.%, simple polyetherpolyols A2) is contained in an amount of ≥1 to ≤10 wt.% and complex polyetherpolyols A3) is contained in an amount of ≥1 to ≤5 wt.%. By such composition polyol as one component, you can obtain a viscous foams with satisfactory durability and compliance with specified dimensions.

An example of the composition of the polyol as one component A) in the method according to the invention is the following structure:

The present invention relates, furthermore, to foams/penopolistirolbeton obtained by the method according to the invention. In order to avoid unnecessary repetitions details of individual variants of their implementation are given in the explanation of the method according to the invention.

The foams according to the invention can be used, for example, in the form of a rigid foam for insulation, in the form of a block of soft foam for mattresses, molded soft foam for car seats and cushions for seats, acoustic foam for sound insulation, as a thermoplastic foam, foam for shoes and microporous foams.

In one embodiment of the invention, the polyurethane/peoplesolidarity according to the invention have a density of ≥30 kg/m³to ≤50 kg/m³(measured according to DIN EN ISO 3386-1-98). Preferably, the density is in the sight of the lah ≥33 kg/m ³to ≤340 kg/m³and, particularly preferably, from ≥35 kg/m³to ≤38 kg/m³.

Metal-containing layered composite materials are a sandwich of layered composite elements consisting of at least two coating layers and located between the layer of the kernel. Metal-containing layered foam laminated composite elements contain, in particular, at least one coating layer of the metal layer and a core of foam plastic, for example, from polyurethane (PUR)rigid foam or polyurethane/polyisocyanurate (PUR/PIR)rigid foam. Such metal-containing layered foam composite elements have long been known from the prior art and are also called metal-containing layered composite elements. Suitable metals are, for example, steel and aluminum.

Examples of the use of such metal-containing layered composite elements are flat or lirovannye the wall elements and profiled elements roofs for industrial buildings and production of refrigerators and LKW-construction, doors for garages or shipping containers.

These metal-containing layered composite elements may be continuous or periodic manner. Device DL is their continuous production of well-known, for example, from German patent DE 1609668 or DE 1247612.

Obtained by using polyurethane foam/penopolistirolbeton (PUR/PIR) according to the invention the metal-containing layered composite elements can be, for example, according to EN 13823 an indicator of General smoke after 600 seconds TSP₆₀₀≥45 m²to ≤60 m².

The metric TSP₆₀₀can also be ≥46 m²to ≤58 m²or ≥47 m²to ≤55 m². In addition, such metal-containing layered composite elements can be an indicator of smoke SMOGRA according to EN 13823 ≥1 m²/S²to ≤10 m²/S²preferably, ≥2 m²/S²to ≤8 m²/S²especially preferably, from ≥3 m²/S²to ≤6 m²/S².

The next object of the present invention is a metal-containing composite layered element comprising a metal layer and a polyurethane/penopoliuretanovymi layer according to the invention. Detailed information about the metal-containing layered composite materials have already been described in connection with the description of the application of the foams according to the invention.

In one embodiment, the metal-containing composite layered element according to the invention it is a General indicator of smoke after 600 seconds TSP₆₀₀≥45 m to ≤60 m²preferably ≥46 m²to ≤58 m²especially preferably, from ≥47 m²to ≤55 m².

In another embodiment, the metal-containing composite layered element according to the invention it is an indicator of General smoke SMOGRA ≥1 m²/S²to ≤10 m²/S²preferably, ≥2 m²/S²to ≤8 m²/S²especially preferably, from ≥3 m²/S²to ≤6 m²/S².

SMOGRA the metric TSP₆₀₀the metric TSP₆₀₀indicator and FIGRA index determined according to standard EN 13823.

Examples

The composition used in the examples of the starting substances:

Phthalic anhydride (PSA): PSA technical, Lanxess Deutschland GmbH,

Adipic acid: adipic acid, BASF,

Diethylene glycol (DEG): DEG, firm Ineos,

EG: EG company Ineos,

The chloride dihydrate divalent tin: the firm Aldrich

Used methods of analysis: Viscometer MCR 51, the company Anton Paar.

A) Obtaining a complex of polyether polyols

Example 1 (single-stage standard way, comparative example).

In a 4-neck flask with a volume of 4 l, equipped with a heating fungus, mechanical stirrer, internal thermometer, tubing with a nozzle height of 40 cm, the upper part of the column, descending intensive cooler and cooled with dry ice sat what MICOM, and diaphragm vacuum pump, placed in the upper flow of nitrogen at 140°C 1437,1 g (9,71 mol) of phthalic anhydride and slowly added 1737,3 g (16,39 mol) of diethylene glycol. After 1 hour the temperature was raised to 180°C, was mixed into 65 mg of the dihydrate salt of divalent tin and the pressure was reduced to 700 mbar. In the next 5 hours the pressure was continuously reduced to a final pressure of 45 mbar. The temperature was raised to 200°C., the pressure was increased to 115 mbar and was completed the reaction at a total length of 27 hours. In the course of the entire reaction, the distillate was collected in a cooled with dry ice collection. By gas chromatography identified the number formed by 1,4-dioxane, equal to 17.6,

Analysis of complex polyester:

Hydroxyl number is 234 mg KOH/g,

Acid number of 1.6 mg KOH/g,

Viscosity - 11300 MPa·s (25°C), 930 MPa·s (50°C)190 MPa·s (75°C),

The amount of formed complex polyetherpolyols - 2982 g,

The number of dioxane in the calculation of the number of complex polyetherpolyols and 17.6 g/2,982 kg=of 5.92 g of dioxane/kg complicated polyester

The number of dioxane in the calculation of the amount of diethylene glycol and 17.6 g/1,738 kg=10,16 g of dioxane/kg diethylene glycol.

Example 2 (two-Stage method according to the invention).

In the apparatus of Example 1 under the upper flow of nitrogen was placed at 180°C 1444 g (9,76 mol) of phthalic anhydride and slow flashing, and than whom but added 1193 g (of 11.26 mol) of diethylene glycol. After 1 hour, the temperature was lowered to 150°C. was Added 356 g (2,44 mol) of adipic acid and 429 g (6,92 mol) of ethylene glycol and cooperated reagents at 200°C for 3 hours. Added 65 g of chloride dihydrate divalent tin and reduced pressures up to 300 mbar. In the next 5 hours continuously reduced pressure to a final value of 80 mbar and was completed the reaction at a total length of 21 hours. In the course of the entire reaction was collected distillate is cooled in dry ice collection. The resultant 1,4-dioxane was identified by gas chromatography as 4.8 g, hydroxyl number 199 mg KOH/g (calculated hydroxyl number of 212 mg KOH/g), the quantity added 160 g (1,51 mol) of diethylene glycol and balanced at normal pressure and 200°C for 5 hours.

Analysis of complex polyester:

Hydroxyl number 239,7 mg KOH/g,

Acid number of 2.1 mg KOH/g,

Viscosity - 8700 MPa·s (25°C), 820 MPa·s (50°C)180 MPa·s (75°C),

The amount of formed complex polyetherpolyols - 3315 g,

The number of dioxane in the calculation of the number of complex polyetherpolyols - 4.8 g/3,315 kg=1.45 g of dioxane/kg complicated polyester

The number of dioxane in relation to the number used

diethylene glycol - 4.8 g/of 1.353 kg=3,55 g of dioxane/kg diethylene glycol.

In the following we use the following expression:

In the expression "weight of ester, of]." theoretical means output complex polyetherpolyols (without side effects) in the calculation of the amount of the original substance.

The expression "weight of ester without dioxane" means the experimentally found the number of received complex polyetherpolyols.

From Tables 1 and 2 clearly shows that the formation of dioxane when using the method according to the invention can be reduced. For example, according to the standard method according to Example 6 is formed of 5.40 g of dioxane per 1 kg of the formed complex polyetherpolyols or 8,83 g of dioxane in the calculation of the quantity used diethylene glycol, while according to Example 7 according to the invention only 0,81 g of dioxane for 1 kg of complex polyetherpolyols or only 2,18 g dio is Sana on 1 kg of used diethylene glycol.

The effects are shown in Table 1 variants differ from the examples of Table 2, mainly hydroxyl number of complex polyetherpolyols.

C. Examples of the preparation of PUR/PIR rigid foam

Examples 8-10

Components used:

(a) complex polyether polyols of comparative Example 1 or Examples 3 or 4 according to the invention;

(b) TCPP, Tris(1-chloro-2-propyl)phosphate, Lanxess GmbH, Germany;

(c) TER, triethyl phosphate, firm Levagard;

(d) additive 1132 Bayer MaterialScience, containing the product of the interaction of phthalic anhydride and diethylene glycol with an acid number of about 97 mg KOH/g;

(e) PET V 657, trifunctionally polietilenoksidnye derived from 1,1,1-trimethylolpropane as starter, with a molecular weight of about 660 daltons company MaterialScience AG;

(f) a stabilizer, copolymerized polyether and polysiloxane, the company Evonik.

Specified in Table 3 additive in the foam (b-f) consists of 20 parts by weight of component (b), 5 parts by weight of component (C)and 2.2 parts by weight of component (d), 5 parts by weight of component (e) and 4 parts by weight of component (f).

Activator (g) salt of carboxylic acid (PIR catalyst): Desmorapid® VP.PU NV 13, Bayer MaterialScience AG, Leverkusen, Germany;

Isocyanate (h) Desmodur® VP.PU 44V70L, polymeric polyisocyanate based on 4,4'-diphenylmethanediisocyanate with NCO-content of about 31.5 wt.%, Bayer MaterialScience AG, Leverkusen, Germany.

In the laboratory room is Ali in a cardboard Cup all source materials according to the recipe for hard foam except for the polyisocyanate component and kept at a temperature of 23°C, mixed by means of a laboratory mixer Pendraulik (for example, type LM-34, firms Pendraulik) and, if necessary, adding a volatile blowing agent (pentane). Then polyol as one of the mixture under stirring was added polyisocyanate component (also thermostated at 23°C), were intensively mixed and the reaction mixture was poured into molds lined with a layer of metallic coating (firm Corns). After 2.5 minutes the indentation method was determined by the rigidity of the foam and after 8-10 minutes was determined by the maximum core temperature. In the next, at least 24 hours was carried out by addition reaction at 23°C, and then has determined the following properties.

BVD test main test respectively Switzerland to determine the degree of Flammability of building materials Society of the control of insurance against fire, edition 1988 and amended in 1990, 1994, 1995 and 2005 (in conjunction with the Society cantonal insurance against fire, Bandesstr. 20, 3011, Bern, Switzerland).

Bond strength: determined by the Department of the foamed coating layer and measuring the necessary forces through spring scales.

Damage: visual assessment of education shells after the formation of the coating layer. Distinguished assessment: "no" (no shells on the area of 1 m²), "small presence (up to 5% of the area has cancer, the guilt) and "strong" pitting (more than 20% of the area has a sink).

Examples 11 and 12

Obtained according to Examples 11 and 12 rigid foams with density (ISO 845) within 40-41 kg/m³showed the following profile of properties:

tensile strength of 0.14 N/mm²(DIN 53292),

module tensile (DIN 53292): 6.4 N/mm²,

stress at compression (DIN 53291): 0,15 N/mm²,

the modulus of elasticity in compression (DIN 53291): 4,3 N/mm²,

the tensile shear strength (DIN 12090): 0,19 N/mm²and

the modulus of elasticity shear (cut) (DIN 12090): 3,8 N/mm².

Hard people is you according to the invention in Examples 11 and 12 were tested regarding the fire resistance according to the Single Burning Item (SBI)test (EN 13823). For this purpose were obtained from standard commercial metal-containing composite layered elements with metal-containing layered composite elements containing rigid foams according to the Examples 11 or 12 (see Examples 17 and 18), as well as foams for comparison (comparative examples 13-16) and tested. Received the results presented in Table 5.

In the case of the FIGRA index (the speed of ignition; the speed of flame propagation) in the class of possible indicators below 250 W/s, and the class of possible indicators below 120 W/s. In the case of indicator THR₆₀₀(the total heat total heat dissipation through 600 sec) rate below 15 MJ belongs to class C, and the rate of less than 7.5 MJ belongs to the class C. Figure SMOGRA (the speed of smoke; the speed of propagation of smoke) less than 180 m²/s²it belongs to the class S2, and a score of less than 30 m²/s²belongs to the class of S1. The metric TSP₆₀₀(total smoke emission; General education smoke after 600 seconds) less than 200 m²it belongs to the class S2, and a score of less than 50 m²belongs to the class of S1.

Obtained using the foam according to the invention IU allstargame composite layered element (Example 17 or 18) inside the test system has the lowest TSP ₆₀₀. In the case of metal-containing layered composite element according to Example 18 metric TSP₆₀₀even reached values 53, and when the repetition of the test - value 47, resulting in a possible classification in the class S1. There is also a low indices THR₆₀₀and SMOGRA. Therefore, in the aggregate, a rigid foam according to the invention exhibits very favorable properties of fire resistance.

1. The method of obtaining complex polyether polyols, in which:
at the stage a) mixing at least one carboxylic acid anhydride (A)selected from the group consisting of phthalic anhydride, anhydride trimellitic acid and anhydride pyromellitic acid, and diethylene glycol (B) and subject to their interaction
moreover, the molar ratio of components (B) to (A) is in the range from 1.5:1.0 to 0.7:1.0, and the total content of components (A) and (B) in calculating the masses of all components of the mixture is in the range from 66 to 90 wt.%,
a to stage b) to the complex polyetherpolyols from stage a) add diethylene glycol (B),
moreover, complex polyetherpolyols from stage a) has a higher molecular weight than the more complex polyetherpolyols from stage b), a complex polyetherpolyols from stage a) has a molecular weight in the range of 1400 and 430 g/mol and a hydroxyl number in the range between 80 and 260 mg KOH/kg,
complex polyetherpolyols from stage b) and EET molecular weight in the range of 750 and 350 g/mol and a hydroxyl number in the range between 150 and 320 mg KOH/kg,
and in stage a) add at least one other glycol (C) with 2-4 carbon atoms with the exception of diethylene glycol and at least one aliphatic dicarboxylic acid (D) with 5-12 carbon atoms, and the number of components (C) and (D) at stage (a) be chosen so that the number of components (A), (B), (C) and (D) in the mixture was 100 wt.%.

2. The method according to claim 1, characterized in that the carboxylic acid anhydride (A) is phthalic anhydride.

3. The method according to claim 1, characterized in that the glycol (C) with 2-4 carbon atoms selected from the group consisting of ethylene glycol, 1,3-propane diol, 2-methyl-1,3-propane diol, 1,2-propane diol, particularly preferably glycol (C) with 2-4 carbon atoms is ethylene glycol.

4. The method according to claim 1, characterized in that the aliphatic dicarboxylic acid (D) with 5-12 carbon atoms selected from the group consisting of glutaric acid, adipic acid, pipelinewall acid, cork acid, azelaic acid, sabatinovka acid, undecadienal acid and dodecadienol acids, preferably dicarboxylic acid (D) with 5-12 carbon atoms are adipic acid or sabotinova acid.

5. The method according to claim 1, characterized in that the molar ratio of components (B) to (A) is in the range from 1.2:1.0 to 0.75 to 1.0 second.

6. The method according to one of claims 1 to 5, characterized in that the total to icesto components (A) and (B) in calculating the masses of all components is in the range between 66 and 90 wt.%.

7. The method of obtaining a polyurethane (PUR) or penopolistirolnyh (PIR) foams, which includes stages:
a) interaction of complex polyetherpolyols received from one or more of claims 1 to 6, with
b) polyisocyanates component,
c) a blowing agent,
d) one or more catalysts,
e) optionally, a flame retardant and/or other auxiliary substances and additives.

8. The use of polyurethane foam (PUR) or penopolistirolbeton (PIR), obtained by the method according to claim 7, to obtain a metal-containing layered composite elements.

9. Metal-containing composite layered element comprising a metal layer and a layer containing PUR or PIR foam obtained by the method according to claim 7.