KR20130004587A - Method for producing polyurethanes - Google Patents

Abstract

The present invention provides a process for preparing a polyurethane comprising the steps of reacting a compound having (a) a polyisocyanate and (b) a compound having two or more hydrogen atoms reacting with an isocyanate group, wherein (b) two reacting with an isocyanate group The compound having the above hydrogen atom is a functional group of 2-8 obtained by the addition of alkylene oxide (b1b) on the compound having two or more hydrogen atoms which react with the alkylene oxide by using amine (b1c) as a catalyst. And at least one polyether alcohol (b1) having a hydroxyl number of 200-600 mgKOH / g.

Description

Manufacturing method of polyurethane {METHOD FOR PRODUCING POLYURETHANES}

The present invention relates to a process (method) for producing a polyurethane by reaction of a polyisocyanate with a compound having two or more hydrogen atoms reacting with an isocyanate group.

Polyurethanes have been known for a long time and are extensively described in the literature. Polyurethanes are typically prepared by reaction of polyisocyanates with compounds having two or more hydrogen atoms that react with isocyanate groups.

Polyurethanes can be used in many technical fields. The starting compounds can be varied to produce polyurethanes with different properties. The polyurethane so provided may be dense or otherwise foamed through the use of a blowing agent.

Because of the limited number of commercially available polyisocyanates, different properties of polyurethanes are preferably achieved by varying compounds having at least two hydrogen atoms that react with isocyanate groups.

The compounds having at least two hydrogen atoms which react with isocyanate groups are in most cases polyfunctional alcohols. Polyester alcohols as well as polyester alcohols have the greatest industrial importance.

Polyether alcohols are mostly prepared by addition of alkylene oxides, preferably ethylene oxide and / or frolene oxide, to the polyfunctional alcohols and / or amines. The addition reaction is typically carried out in the presence of a catalyst.

All such processes are known to those skilled in the art.

Improving the processing and product properties of polyurethanes has been a continuing goal. This is basically possible through the modification of polyether alcohols, as described. Such modification can be carried out in the nature of the polyol itself used, but can also be carried out through the use of added materials.

It is an object of the present invention to provide a process for producing polyurethanes characterized by improved flowability of the components. The components must have a very low viscosity and be efficiently pumpable at low temperatures. The components should still have a processable viscosity after loading with the filler. Moreover, the components should have good solubility in blowing agents, more specifically in hydrocarbons, and improved compatibility with isocyanates. The resulting polyurethane should have a low release and uniform structure, more specifically free of voids and defects at the surface.

The inventors have surprisingly found that the object is achieved by using a polyol component comprising at least one polyether alcohol obtained using an amine as a catalyst.

US 20070203319 and US 20070199976 describe polyether alcohols obtained by the addition of alkylene oxides with dimethylethanolamine on starting materials comprising solid compounds at room temperature. However, polyutethetans obtained using such polyols are not described.

Accordingly, the present invention provides a process for preparing a polyurethane comprising (a) reacting a polyisocyanate with (b) a compound having at least two hydrogen atoms reacted with an isocyanate group, wherein (b) isocyanate A compound having two or more hydrogen atoms reacting with a group is reacted with an alkylene oxide (on a compound having two or more hydrogen atoms, also referred to as starting materials, later reacted with an alkylene oxide by using an amine (b1c) as a catalyst). at least one polyether alcohol (b1) having a functionality of 2-8 and a hydroxyl number of 200-800 mgKOH / g, obtained by the addition of b1b).

The polyether polyols (b1) can be used as the compound of component (b) alone.

Preferably, the polyether polyols (b1) are used in amounts of 10-90% by weight, based on the weight of component (b).

Preferably, compounds having at least two hydrogen atoms reacted with alkylene oxides used to prepare the polyether alcohols (b1) include mixtures comprising at least one compound (b1ai) which is solid at room temperature.

Compounds of this type are known and frequently used in the preparation of polyether polyols, especially those for use in rigid polyurethane foams. The compounds include trimethylolpropane, pentaerythritol, glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols, for example oligomer condensation products of phenol and formaldehyde, oligomer condensation products of aniline and formaldehyde (MDA), toluene It is preferably selected from the group consisting of diamines (TDA) and Mannich condensates of phenol, formaldehyde and dialkanolamines, and also mixtures of melamine and also two or more of the alcohols listed.

In a preferred embodiment of the invention, compound (b1ai) is selected from the group consisting of sucrose, sorbitol and pentaerythritol, more preferably from sucrose or sorbitol. In a particularly preferred embodiment of the invention, compound (b1ai) is sucrose.

The aromatic amine used as compound (b1ai) is more specifically selected from toluenediamine (TDA) or diphenylmethane diisocyanate (MDA) or polymer MDA (p-MDA). In the case of TDA, more specifically it is the 2,3- and 3,4- isomers used (also referred to as Bisinal TDA).

Useful starting materials (b1a) further include compounds having at least two hydrogen atoms that react with an alkylene oxide comprising at least one compound (b1aii) that is liquid at room temperature.

In a preferred embodiment of the invention, the starting material of component (b1) comprises a room temperature liquid compound (b1aii) comprising an alkylene oxide as well as a hydrogen atom reacting with compound (b1ai).

Compound (b1aii) may comprise an alcohol or an amine. They more particularly have 1 to 4, preferably 2 to 4 hydrogen atoms that react with alkylene oxides.

Compound (b1aii) is glycerol, monofunctional alcohol of 1-20 carbon atoms, ethanol, propylene glycol and higher homologues thereof, ethylene glycol and feed homologues thereof, and also mono-, di- and tri-alkanolamines, more Specifically it is preferably selected from glycerol.

In a further embodiment of the invention, component (b1a) comprises a mixture of one or more room temperature solid amines (b1ai) and room temperature liquid alcohols (b1aii). It is preferred that the room temperature solid alcohol (b1ai) can comprise MDA and polymer MDA. The room temperature liquid alcohol (b1aii) is preferably capable of containing ethylene glycol and its higher homologs and propylene glycol and its higher homologs. The concentration of its amine homologues in p-MDA depends on the process conditions. In general, the distribution (% by weight) is as follows:

2 rings MDA: 50-80% by weight

3 rings MDA: 10-25% by weight

4 rings MDA: 5-12 wt%

At least 5 rings MDA: 5-12% by weight.

Preferred p-MDA mixtures have the following composition:

2 rings MDA: 50% by weight

3 rings MDA: 25 wt%

4 rings MDA: 12 wt%

5 or more rings MDA: 13% by weight

Further preferred p-MDA mixtures have the following composition:

2 rings MDA: 80% by weight

3 rings MDA: 10% by weight

4 rings MDA: 5 wt%

5 or more rings MDA: 5% by weight

In a further preferred embodiment of the invention, component (b1a) comprises a mixture of at least one room temperature solid alcohol (b1ai) and at least one room temperature liquid alcohol (b1aii). The room temperature solid alcohol (b1ai) preferably comprises sugar alcohols, more particularly those characterized above, even more particularly sucrose. The room temperature liquid compounds (b1aii) are glycerol, monofunctional alcohols having 1-20 carbon atoms, ethanol, propylene glycol and higher homologues thereof, ethylene glycol and feed homologues thereof, and also mono-, di- or tri-alkanes It is preferable to include at least one compound (b1aii) selected from the group consisting of olamines, more specifically glycerol. Component (b1a) may also comprise water. If water is used, the amount is more specifically 25% by weight or less based on the weight of component (b1a).

Room temperature liquid compounds (b1aii), as mentioned, may also include compounds having hydrogen atoms that react with alkylene oxides and having from 1-20 carbon atoms. Preference is given here to monofunctional alcohols, methanol, ethanol, propanol, octanol, dodecanol.

The alkylene oxide (b1b) preferably comprises propylene oxide, ethylene oxide, butylene oxide, isobutylene oxide, styrene oxide and mixtures of two or more thereof. Preferably, as the alkylene oxide (b1b), propylene oxide, ethylene oxide or a mixture of propylene oxide and ethylene oxide is used. As alkylene oxide (b1b), it is especially preferable to use propylene oxide.

Catalyst (b1c), as mentioned, comprises amines other than component (b1ai) and component (b1aii). This amine may comprise primary, secondary or tertiary amines and also aliphatic or aromatic amines, more specifically tertiary amines. In further embodiments, aromatic heterocyclic compounds having at least one, and preferably one, nitrogen atom in the ring may be involved.

The amine (b1c) is trialkylamine, more specifically trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylalkylamine, more specifically dimethylethanolamine, dimethylethoxyethanolamine, dimethylcyclohexylamine, dimethyl Ethylamine, dimethylbutylamine, aromatic amine, more specifically dimethylaniline, dimethylaminopyridine, dimethylbenzylamine, pyridine, imidazole (more specifically imidazole, N-methylimidazole, 2-methylimidazole, 4 -Methylimidazole, 5-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 1-hydroxypropylimidazole, 2,4,5-trimethyldi Midazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, N-phenylimidazole, 2-phenylimidazole, 4-phenylimidazole), guanidine, alkylated guanidine (more specific 1,1,3,3-tetramethylguanidine), 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, ah Dine (more specifically 1,5-diazo-bicyclo [4.3.0] non-5-ene, 1,5-diazabicyclo [5.4.0] undec-7-ene) It is preferable to be.

It is also possible to use mixtures of two or more of the amines mentioned as catalysts.

In a preferred embodiment of the invention, the catalyst (b1c) is dimethylethanolamine.

In a preferred embodiment of the invention, the catalyst (b1c) is imidazole.

Here, the amine is preferably used in an amount of 0.01-5.0 mass%, preferably 0.05-3.0 mass%, more preferably 0.1-1.0 mass%, based on the total batch.

To prepare the polyether polyol (b1), the constituents (b1a and b1c) of the starting material mixture are typically introduced into the reactor and mixed together. Subsequently, the mixture therein is inertly treated. Thereafter, alkylene oxide is metered in.

The addition reaction of the alkylene oxide is preferably carried out at a temperature of 90 to 150 ℃ and a pressure of 0.1 to 8 bar. Metered dose of alkylene oxide is typically followed by a postreaction phase to terminate the reaction of alkylene oxide.

Following the end of the metering of the alkylene oxide, a post-reaction step is typically performed which terminates the reaction of the alkylene oxide. The post-reaction step is carried out if necessary. Subsequently, distillation is typically performed to remove volatiles, which is preferably carried out under reduced pressure.

The amine catalyst (b1c) can be maintained in the polyether alcohol. This simplifies the process for producing it, since the removal of the catalyst required when oxides and hydroxides of alkali metals are used is no longer necessary. This leads to an improvement in space time efficiency. Salt removal by filtration forms a filter cake. The polyol loss in the filter cake generally amounts to several percent. The improved space time yield and the amount of filter loss avoided contribute to reduced manufacturing costs.

Combinations of alkali metal hydroxide catalysts and amine catalysts are also useful. In particular, this is an option to prepare dihydroxyhydric polyols. The resulting product can be post-treated similarly to polyols catalyzed by alkali metal hydroxides. Alternatively, the product can be worked up by performing just before the neutralization step with acid. In such cases, preference is given to using carboxylic acids, for example lactic acid, acetic acid or 2-ethylhexane.

The amine catalyst (b1c) may itself be alkoxylated in the course of the reaction. Therefore, the alkoxylated amines have a higher molecular weight and reduced volatility of later products. Because of the remaining auto-reactivity of the alkoxylated amine catalysts, incorporation into the polymer scaffold occurs during later reactions with isocyanates. The self-reactivity of the formed tertiary amines impart self-reactivity to polyols that can be usefully employed in certain applications.

Without wishing to be bound by any theory, the polyether alcohols obtained using amines as catalysts have a different composition than that of polyether alcohols obtained using other catalysts. Such other molecular configurations benefit from the production of polyurethanes.

Therefore, the polyols of the present invention have obvious benefits in polyurethane applications, in particular in the manufacturing process of polyurethane foams.

As mentioned, polyether alcohols (b1) are used in the preparation of polyurethanes.

Starting materials used therein may be described in more detail as follows.

The organic polyisocyanate (a) contemplated is preferably an aromatic polyfunctional isocyanate.

Specific examples include 2,4- and 2,6-tolylene diisocyanate (TDI) and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate (MDI) And corresponding isomeric mixtures, mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanates, and in the preparation of rigid polyurethane foams, in particular 4,4 ', 2,4'- and 2, 2'-diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate (crude MDI).

The polyether alcohols of the present invention are typically used in admixture with other compounds having two or more hydrogen atoms that react with isocyanate groups.

The compounds used together with the polyether alcohols (b1) having at least two hydrogen atoms which react with isocyanates as used according to the invention are in particular polyether alcohols and / or polyesters having an OH number in the range of 100 to 1200 mgKOH / g. Contains alcohol.

The polyester alcohols used together with the polyether alcohols (b1) used according to the invention are generally polyfunctional alcohols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, preferably diols and 2 To 12 multifunctional carboxylic acids, for example succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decandicarboxylic acid, maleic acid, fumaric acid, preferably phthalic acid, isophthalic acid , By condensation with terephthalic acid and isomer naphthalenedicarboxylic acid.

The polyether alcohols used with the polyether alcohols (b1) used according to the invention generally have a functionality of 2 to 8, more specifically 3 to 8.

Particular preference is given to using polyether alcohols prepared by known methods, for example by anionic polymerization of the alkali oxides in the presence of a catalyst, preferably an alkali metal hydroxide.

Alkylene oxides used are mostly ethylene oxide and / or propylene oxide, preferred pure 1,2-propylene oxide.

The starting materials used are especially compounds having at least 3, preferably 4 to 8 hydroxyl groups, or at least 2 primary amino groups in the molecule.

Examples of starting molecules having at least 3, preferably 4 to 8, hydroxyl groups in the molecule include trimethylolpropane, glycerol, pentaerythritol, for example sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols , Resols, for example condensation products of phenol and formaldehyde, aniline and formaldehyde condensation products (MDA), toluenediamine (TDA) and Mannich condensates of phenols, formaldehyde and dialkanolamines and also melamines It is preferable.

The polyether alcohols have a functionality of 3 to 8, and preferably a hydroxyl value of 100 mgKOH / g to 1200 mgKOH / g, more preferably 120 mgKOH / g to 570 mgKOH / g.

By using a bifunctional polyol having a molecular weight in the polyol component in the range from 500 to 1500, for example polyethylene glycol and / or polypropylene glycol, the viscosity of the polyol component can be adapted.

Compounds having two or more hydrogen atoms that react with isocyanates include chain extenders and crosslinkers optionally used. Rigid polyurethane foams can be prepared with and without the use of chain extenders and / or crosslinkers. The addition of bifunctional chain extenders, trifunctional and at least four functional crosslinkers or optionally also mixtures thereof may prove advantageous for modifying mechanical properties. The chain extenders and / or crosslinkers used are alkanolamines, more particularly diols and / or triols, having a molecular weight in the range of up to 400, preferably in the range from 60 to 300.

The chain extenders, crosslinkers or mixtures thereof are advantageously used in amounts of 1 to 20% by weight, preferably 2 to 5% by weight, based on the polyol component.

Polyurethane foams are typically prepared in the presence of a blowing agent. The blowing agent used may preferably be water and react with isocyanate groups by removal in carbon dioxide. A further frequently used chemical blowing agent is formic acid, which reacts with isocyanates by releasing carbon monoxide and carbon dioxide. So-called physical blowing agents may also be used in addition to or instead of chemical blowing agents. Physical blowing agents generally include room temperature liquid components that are inert to the feed components and vaporize under the conditions of the urethane reaction. The boiling point of such a compound is preferably 50 캜 or lower. Physical blowing agents also include compounds which are gaseous at room temperature and introduced and / or dissolved into the feed component, such as carbon dioxide, alkanes, more specifically low boiling alkanes and fluoroalkanes, preferably alkanes, more specifically low boiling alkanes And fluoroalkanes.

Physical blowing agents are generally alkanes and / or cycloalkanes having 4 or more carbon atoms, dialkyl ethers having 1 to 8 carbon atoms, esters, ketones, acetals, fluoroalkanes and 1 to 3 carbon atoms in the alkyl chain. Tetraalkylsilanes having more preferably are selected from the group comprising tetramethylsilane.

Examples are propane, n-butane, isobutane, cyclobutane, n-pentane, isopentane, cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone, and also to be degraded in the troposphere. Fluoroalkanes which are harmful to the ozone layer, such as trifluoroethane, difluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1,1,2-tetrafluoroethane, difluoroethane and 1,1,1,2,3,3,3-heptafluoropropane, and also perfluoroalkanes such as C3F8, C4F10, C5F12, C6F14, and C7F16. Particular preference is given to using pentane, more particularly cyclopentane. The physical blowing agents mentioned can be used alone or in any desired combinations with one another.

In a preferred embodiment of the invention, mixtures of physical and chemical blowing agents can be used. Preference is given to using mixtures of physical blowing agents and water, more particularly mixtures of hydrocarbons and water. Among the hydrocarbons, pentane is particularly preferable, and cyclopentane is particularly preferable among the pentanes.

The preparation of the polyurethanes can be carried out, if necessary, in the presence of catalysts, flame retardants and also conventional auxiliaries and / or added materials.

Further details regarding the starting materials used can be found in, for example, Kunststoffhandbuch, volume 7 “Polyurethane”. edited by Gunter Oertel, Carl-Hanser-Verlag Munich, 3rd edition, 1993.

The polyurethanes obtained by the process of the present invention more specifically comprise foamed polyurethanes, more preferably rigid foams. In one specific embodiment of the present invention, the rigid foams have a dense skin and a cellular core, and are often known as integral skin rigid foams or high density structural foams. Such foams are typically made in a closed mold in the presence of a blowing agent. The combination of pressure and mold temperature makes the surface of the foam densely skinned. Such foams have many uses, for example in automotive trim and spoiler portions, profiles, for example profiles for windows, fittings, computer housings and filter pressure plates. The surface quality of the foam is important for such use.

The rigid foams include, for example, those used for thermal insulation. Here, the good compatibility of the polyether alcohol (b1) with the blowing agent and the good flow behavior are advantageous. Here good general compatibility between polyol mixtures and isocyanates is advantageous. Poor polyol / isocyanate compatibility can lead to separation of reaction components in certain circumstances, especially in systems involving long reaction times, which in turn results in coarse cellity to the foam and poor adhesion of the foam to the substrate. May cause

Further embodiments of the present invention use rigid foams in automotive configurations, for example in engine compartments or in interiors. In the event of an accident, there are engine compartments designed to absorb energy. Rigid foams are used in interiors for back-foaming polymer sheets, such as vinyl sheets. This is the case, for example, with side door trims or dashboards. The main advantage of the polyurethanes obtained by the process of the present invention here lies in the lower fogging.

Another advantage for reduced fogging is that due to the self-reactivity of the polyether polyol (b1), the amount of use of the catalyst that is the source of fogging can be reduced.

A specific requirement in integral skin rigid foams, also referred to as thermoset foams, is the good compatibility of the polyether alcohols (b1) with blowing agents, in particular hydrocarbons such as cyclopentane.

The manufacture of thermosetting foams often uses additional fillers. One group of fillers is those having flame retardant properties, such as ammonium polyphosphate, red phosphorous or aluminum trihydrate.

A further class of fillers are inorganic salts such as calcium carbonate, calcium sulfate or barium sulfate.

Further industrially important fillers are ground glass fibers, carbon fibers, carbon nanotubes, glass microspheres, silicon, carbon black, wollastonite, talc, clays, pigments such as titanium dioxide.

The following examples illustrate the invention.

Preparation of Polyols:

Example  1 (invention):

A 960 L pressure reactor equipped with a stirrer, a jacket for heating and cooling, a metering unit for solid and liquid materials including alkylene oxide and also a device for nitrogen deactivation and vacuum system was heated to 80 ° C. to dry and nitrogen was Deactivated repeatedly. 102.75 kg of glycerol were added, the stirrer was started and 154.3 kg per metered. The reactor was heated to 95 ° C. After addition of 6.03 kg of DMEOA, metering of 541.57 kg of PO was started and the reactor temperature was increased to 112 ° C by the heat of reaction. After 3 hours of reaction termination time at 90 ° C., the product was stripped at 100 ° C. under a nitrogen stream to give 776 kg of polyol having the following specifications:

Hydroxyl number 483 mg KOH / g

Viscosity 6600 mPas, 25 ° C

Water content 0.023%

Example  2( Comparative example ):

A 960 L pressure reactor equipped with a stirrer, a jacket for heating and cooling, a metering input device for solid and liquid materials including alkylene oxide, and also a device for nitrogen deactivation and vacuum system, heated to 88 ° C., dried and repeatedly Deactivated with nitrogen. 91.18 kg of glycerol were added and the stirrer was started. Then, 3.32 kg 48% KOH and 139.82 kg sucrose were added. 96.91 kg of PO was metered at 105 ° C. After 2 hours of reaction, the product was stripped at 100 ° C. with nitrogen and then mixed with water, neutralized with 80% phosphoric acid and filtered. The yield was 682 kg of polyol with the following characteristics in analysis:

Hydroxyl number 497 mg KOH / g

Viscosity 8400 mPas, 25 ° C

Water content 0.016%

Potassium 35.7 ppm

Viscosity of the polyol and polyol mixtures is measured using a Rheotec RC 20 rotary viscometer with a spindle CC 25 DIN (spindle diameter: 12.5 mm; measuring cylinder inner diameter: 13.56 mm) at a shear rate of 50 1 / s, unless stated otherwise It was measured at 25 ℃.

The hydroxyl value was measured according to DIN 53240.

Determination of pentane solubility:

50 g of polyol or polyol mixture were introduced into a 100 mL glass vessel. An amount of cyclopentane was added. The glass container was then sealed, vigorously shaken for 5 minutes and then left to stand for 1 hour. Thereafter, the appearance of the sample was examined. When the sample was clear, the test was repeated with a smaller amount of cyclopentane. In this way, the maximum amount of cyclopentane soluble in the polyol or polyol mixture was measured. This amount was the pentane solubility of the polyol or polyol mixture. The accuracy of this method was 1%.

Polyols Used Polyol Starting material catalyst Hydroxyl Pentane solubility Viscosity mgKOH / g % [mPas] One Sucrose / glycerol PO, Fn = 4.3 DMEOA 483 12 6600 2 Sucrose / glycerol PO, Fn = 4.3 KOH 497 <10 8400 3 Glycerol PO KOH 230 Irrelevant Irrelevant Fn-average functionality
PO-propylene oxide

Isocyanate Compatibility:

Polymeric MDIs such as Lupranat® M20 (BASF SE) (isocyanate (I)) and the polyols used in the process of the present invention were typically immiscible. The 4,4'-MDI main component prepolymer having an NCO content of 23% by weight, commercially available as isocyanate (II), Lupranat® MP102, was fully miscible with such polyols. The mixture of isocyanate (I) and isocyanate (II) may or may not be miscible with such polyols depending on their mixing ratio. This was the basis of the method for measuring the miscibility of polyols and isocyanates. A modified procedure was performed as follows: 1.00 g of polyol was placed on a watch dish 4 cm in diameter. Thereafter, 1.00 g of a mixture of isocyanate (I) and isocyanate (II) was added, followed by stirring with spepula for 1 minute, which was stirred to prevent bubbles from forming. One minute after the end of stirring, the sample was visually inspected. If the mixture was cloudy, the test was repeated using a larger proportion of isocyanate (II) in the mixture. If the mixture was clear, the test was repeated using a smaller proportion of isocyanate (II) in the mixture. In this way, the maximum amount of isocyanate (I) in the mixture was measured while the mixture remained transparent. The accuracy of measuring the amount of isocyanate (I) in the mixture was 2%.

In the case of polyol 1 of the present invention, the mixing ratio of isocyanate I: II was 15/85. In the case of the comparative polyol, the mixing ratio of isocyanate I: II was 5/95.

Example  3: rigid foam applications

Manufacture of foam for mechanical testing

A base foam system comprising 100 pbw of polyol or polyol mixture, 2.4 pbw of Tegostab® B 8467 surfactant (Goldschmidt) and 0.85 pbw of water was used at the starting point. Dimethylcyclohexylamine and cyclopentane were used as catalyst and blowing agent, and polymer MDI (Lupranat® M20, BASF SE) was used as isocyanate. Foams were prepared at isocyanate index 100. The starting material was mixed manually. The amount of dimethylcyclohexylamine was such that the gel time of the foam was 55 seconds. The amount of cyclopentane was such that the free foam density of the foam was 35 kg / m. With this recipe, 500 g of foam samples were prepared in a 11.4 L cube steel mold. The sample was released after 20 minutes. The samples were then stored for 3 days before being tested. Density was measured according to ISO 845 standard and compressive strength was measured according to ISO standard.

Foam formulation Polyol 1 part 100 Polyol 2 part 100 Tegostab B 8467 part 2.4 2.4 DMCHA part 5 5.2 Distilled water part 0.85 0.85 CP part 14.5 14.8 Cup test Setting time s 55 56 density kg / m ³ 38 38 Cube Shape Mold Compressive strength / stress N / mm ² 0.27 0.28 Core density kg / m ³ 34.5 35

In the description of Table 2, upon foam formation, the polyols of the present invention exhibited autocatalytic properties and required less catalyst and less catalyst to reach the same density.

Example  4: Heat curing  Usage

Effect of Catalyst Volume on Reactivity Polyol 1 Weight portion 87.7 87.7 87.7 Polyol 2 Weight portion 87.7 87.7 87.7 Forylol 3 Weight portion 7.8 7.8 7.8 7.8 7.8 7.8 Tegostab b 2219 Weight portion 1.5 1.5 1.5 1.5 1.5 1.5 tap water Weight portion 1.9 1.9 1.9 1.9 1.9 1.9 Dabco 33 LV Weight portion 1.1 1.1 0.5 0.5 0.25 0.25 Cup test Set time s 133 94 305 150 540 190

In the description of Table 3, upon foam formation, the inventive polyols exhibited self catalysis and required less catalyst than polyols not of the invention. This effect was increased by lower catalyst concentrations.

Effect of Fillers on Viscosity Polyol 1 Weight portion 87.7 83.3 78.9 70.2 Polyol 2 Weight portion 87.7 83.3 78.9 70.2 Polyol 3 Weight portion 7.8 7.8 7.4 7.4 7.0 7.0 6.2 6.2 Tegostab b 2219 Weight portion 1.5 1.5 1.4 1.4 1.4 1.4 1.2 1.2 tap water Weight portion 1.9 1.9 1.8 1.8 1.7 1.7 1.5 1.5 Dabco 33 LV Weight portion 1.1 1.1 1.0 1.0 1.0 1.0 0.9 0.9 CaCO ₃ Weight portion 0.0 0.0 5.0 5.0 10.0 10.0 20.0 20.0 Viscosity at 20 ° C mPas 8200 6700 9100 7300 9800 8000 12000 9700

Polyol viscosity was measured according to ISO 3219 at 20 ° C. In the description of Table 4, viscous fillers were added. The inherent viscosity of the polyols of the present invention was also measurable in the packed system.

Plate manufacturer:

Component A was prepared and left at rest for at least 1/2 hour. After addition of the isocyanate, the mixture was mechanically stirred for 13 s at the maximum stirring speed. This mixture was then poured into a hot mold ((20 × 15 × 1 cm) at 50 ° C. After 5 minutes, the plate was released.

Foam prescription and mechanical properties of the plate system One 2 Polyol 1 87.7 Forylol 2 87.7 Polyol 3 part 7.8 7.8 Tegostab b 2219 part 1.5 1.5 tap water part 1.9 1.9 Dabco 33 LV part 1.1 1.1 plate density kg / m ³ 285 280 Shore D Hardness 30 30 Bending strength / stress N / mm ² 8.3 8.1 sag mm 20.6 20.2

Evaluation of Surface Quality:

A sheet of A4 paper was placed on the plate and traced with a round carbon rod using the plate side. The sheet was placed in a scanner, binarized to a limited threshold, and small pixels were removed. Then, the area ratio of the (black) elevation was measured. The high rate was 1% for System 1 (invention) and 22% for System 2 (prior art).

Claims (19)

(a) reacting a polyisocyanate with (b) a compound having two or more hydrogen atoms reacting with an isocyanate group, the method for producing a polyurethane, wherein (b) at least two hydrogen atoms reacting with an isocyanate group Compounds having 2 to 2-8 functionality obtained by addition of alkylene oxides (b1b) on compounds having two or more hydrogen atoms reacting with alkylene oxides by using amines (b1c) as catalysts And at least one polyether alcohol (b1) having a hydroxyl number of 200-600 mgKOH / g. The process according to claim 1, wherein the polyether polyol (b1) is used in an amount of 10-90 wt% based on the weight of the component (b). The compound of claim 1, wherein the compound having at least two hydrogen atoms reacted with the alkylene oxide used to prepare the polyether alcohol (b1) comprises a mixture comprising at least one compound (b1ai) that is solid at room temperature. Phosphorus manufacturing method. The compound (b1ai) according to claim 1, wherein the compound (b1ai) is a pentaerythritol, glucose, sorbitol, mannitol, sucrose, polyhydric phenol, resol, a condensate of aniline and formaldehyde, toluenediamine, phenol, formaldehyde and dialkanolamine Mannich condensate, melamine and also a process comprising a mixture of two or more of these cited compounds. The method of claim 1, wherein the compound (b1a) is selected from the group comprising sucrose, sorbitol and pentaerythritol. The compound (b1a) having at least two hydrogen atoms reacted with the alkylene oxide used to prepare the polyether alcohol (b1) comprises a mixture comprising at least one compound (b1aii) which is liquid at room temperature. It will contain. The compound (b1aii) according to claim 1, wherein the compound (b1aii) comprises glycerol, a monofunctional alcohol having 1-20 carbon atoms, propylene glycol and its higher homologs, ethylene glycol and its feed homologues, and also mono-, di- or tri A production method selected from the group comprising alkanolamines. The process according to claim 1, wherein the compound (b1a) comprises a mixture of at least one compound (b1ai) which is solid at room temperature and at least one compound (b1aii) which is liquid at room temperature. The method of claim 1, wherein the amine (b1c) is selected from the group comprising trialkylamine, aromatic amine, pyridine, imidazole, guanidine, alkylated guanidine, amidine. A process according to claim 1 which is carried out in the presence of a blowing agent (c). The process according to claim 1, wherein water is used as the blowing agent. The process of claim 1 wherein a physical blowing agent is used. The method of claim 1, wherein said physical blowing agent is selected from the group comprising alkanes and fluoroalkanes. The process of claim 1 wherein the preparation is carried out in the presence of a filler. The method of claim 1 wherein said filler is an inorganic salt. The method of claim 1, wherein the filler is selected from the group comprising ammonium polysulfate, red phosphorus and aluminum trihydrate. The method of claim 1, wherein the filler is ground glass fiber, carbon fiber. And carbon nanotubes, glass microspheres, silicon, carbon black, wollastonite, talc, clays and pigments. The method of claim 1, wherein the polyurethane foam is made in a closed mold. Polyurethane obtainable according to any one of claims 1 to 16.