JPH0148288B2 - - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing polyurethane.

Polyurethane foams are produced by reacting polyols with polyisocyanates in the presence of a blowing agent and usually one or more additives other than the blowing agent.

It is known to use preformed polymer-modified polyols, ie, polyols containing additional polymeric materials, in polyurethane-forming reactions to modify the physical properties of the resulting foam in the desired manner. be. Thus, for example, GB 1501172 describes the use of polyol dispersions which are polyaddition products of polyisocyanates and primary amines, secondary amines hydrazines or hydrazides. GB 1482213 also describes the use of polyols in which polymeric substances obtained during the polymerization of ethylenically unsaturated monomers are dispersed and also copolymerized.

The primary object of the present invention is to provide a process for the production of useful polyurethanes using further polymer-modified polyols that may be useful in polyurethane production.

According to the invention, therefore, an alkanolamine is polymerized with an organic polyisocyanate in the presence of a polyol, in which case the alkanolamine is at least predominantly, if not entirely, polyfunctionally reacted with the isocyanate. Provided are methods for producing useful polyurethanes using polymer-modified polyols. That is, this is because by reacting an alkanolamine and an isocyanate in the presence of a polyol at the ratio disclosed herein, the nitrogen atom of the alkanolamine makes the alkanolamine more reactive than the isocyanate. .

In the process of the invention, an alkanolamine [which has one or more hydroxy groups (-OH)]
and primary, secondary or tertiary amines may be used, but 1
one or more amine groups (-NH ₂ , =NH, ≡
N)] acts as a polyfunctional reactive agent, and the polyaddition product combines the alkanolamine with a polyisocyanate (which refers to a compound with two or more isocyanate groups). meaning).
If the alkanolamine is a primary or secondary amine, it has an amine group and an alcohol group, all with hydrogens that are reactive with respect to isocyanates. If the alkanolamine is a tertiary amine, it has multiple alcohol groups with hydrogens all reactive with respect to isocyanates. In any of the above cases,
All or part of the active hydrogen can actually react. In the polyaddition reaction, a combination of an isocyanate and a hydroxyl group forms a urethane bond (-NH-CO-O-), and a combination of an isocyanate and an amine group forms a urea bond (-NH
-CO-NH- or =N-CO-NH-) is thought to lead to linear and/or branched chains. The polyadduct can be mixed with and/or chemically combined (eg, by copolymerization) with a polyol. The term "polymer-modified polyol" as used herein includes both physical and chemical combinations, as well as the coexistence of both, although physical combinations are usually predominant in the method of the present invention. Please keep in mind that this is intended to encourage people. Such a physical combination is
Depending on the starting materials used, the polyaddition product can be in the form of a polyol solution or a stable polyol dispersion. In particular, the physical state of the polymer-modified polyol can be determined by a suitable selection of the alkanolamine and, if appropriate, a suitable selection of the polyol.

In carrying out the process of the invention, in the presence of a polyether polyol with a molecular weight in the range from 200 to 10,000 (in particular from 2,800 to 7,000), the ratio of alkanolamine to isocyanate is approximately 1.0 to 0.5 to 1.0.
The alkanolamine and polyisocyanate that were mixed at a molar ratio of 1.6 and reacted together,
Most advantageously 1 to 35% by weight, based on the weight of the polyol.

Alkanolamines or mixtures of alkanolamines may suitably be used as alkanolamines according to the process of the present invention; these alkanolamines include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, N-methylethanol. Amine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylisopropanolamine, N-ethyl Isopropanolamine, N
-The first, such as propylisopropanolamine,
Includes secondary and tertiary alkanolamines. The term "alkanolamine" as used herein also includes substituted alkanolamines; for example, primary or secondary alkanolamines substituted with halogen at the nitrogen atom moiety or alkyl group moieties may be used. It is also possible to use secondary or tertiary alkanolamines which are halogen-substituted, ie the alcohol group is replaced by a halogen atom. In a particularly preferred embodiment, triethanolamine is used as alkanolamine.

The process according to the invention is carried out using alkanolamines, in particular open-chain aliphatic alkanolamines, but also other alkanolamine compounds, such as those which contain carbocyclic, aromatic or heterocyclic nuclei or a plurality of these nuclei (or ) It is also possible to use alkanolamine compounds having hydroxy groups and amine groups bonded to these nuclei and to open-chain aliphatic nuclei.

Appropriate organic polyisocyanates can be used, including aliphatic, alicyclic, araliphatic, and aromatic polyisocyanates known for polyurethane formation reactions between polyisocyanates and polyols. and heterocyclic polyisocyanates (see, for example, GB 1453258).

Suitable polyisocyanates that are readily available on the market include 2,4 and 2,6-tolylene diisocyanate and mixtures of these isomers (commonly referred to as TDI), prepared by condensing aniline with formaldehyde and then Polyphenylpolymethylene polyisocyanates of the type obtained by phosgene treatment (commonly referred to as crude MDI) as well as carbodiimide groups, urethane groups,
There are polyisocyanates (commonly referred to as polyisocyanates) containing allophonate, isocyanate, urea or biuret groups.

Any suitable polyol can be used, and these polyols have a molecular weight of 200 to 200.
10,000 and which are known for the reaction of polyisocyanates and polyols to form polyurethanes, such as those described in GB 1,482,213. Such known polyols can be obtained by reacting alkylene oxides with active hydrogen-containing compounds, the molecular weight of the reaction product depending on the molecular weight of the alkylene oxide with which the reaction is caused.

The polyaddition products obtained in carrying out the process of the invention can be modified using proportional amounts of monofunctional isocyanates, amines or N-dialkylalkanolamines. For example, the average molecular weight of the polyaddition product is 25 mol% of the above type of monofunctional compound based on the alkanolamine component.
It can be adjusted by combining the ratios up to this point.

Suitable monofunctional isocyanates include methyl isocyanate, isopropylisocyanate,
Isobutyl isocyanate, hexyl isocyanate, lauryl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, tolyl isocyanate,
The isocyanates include 4-chlorophenyl isocyanate and diisopropylphenyl isocyanate.

Suitable monofunctional amines are dialkylamines, including dialkylamines such as dimethylamine, diethylamine, dibutylamine and cyclohexylamine, and suitable N-dialkylalkanolamines are dimethylethanolamine and diethylethanolamine. dialkylalkanolamines including

It is not necessary that all of the alcohol and/or amine groups of the alkanolamine used in the polyaddition reaction of the present invention react with the isocyanate under all conditions, and therefore in some cases the alkanolamine may react monofunctionally. It can also itself act as a main chain extension reaction terminator.

If necessary, the polyaddition reaction according to the invention can be accelerated by the addition of materials such as those conventionally used as catalysts for polyurethane-forming reactions of polyisocyanates and polyols. For this purpose, tin octoate, dibutyl-tin dilaurate and/or amines such as triethylenediamine can be used. The amount of catalyst used can be small compared to the amounts typically used in polyurethane forming reactions, for example in amounts as low as 0.02% of the total weight of the polyol, rather than as high as 0.2%. be able to. However, if necessary, the amount added can be increased.

Although reactions using primary or secondary alkanolamines may not require a catalyst, the use of a catalyst may be advantageous when using a tertiary alkanolamine such as triethanolamine.

The molecular weight of the polyaddition product can be adjusted by varying the quantitative ratio of alkanolamine on the one hand to polyisocyanate on the other hand, and also by varying the amount of monofunctional components, if used. Thus, for example, the molar ratio of alkanolamine to polyisocyanate is 1.0 to
A ratio of 0.5 to 1.0 to 1.6 is preferred, and approximately equimolar amounts are particularly preferred, provided that high viscosities and rapid gelation, which tends to occur with high isocyanate proportions, are suitably tolerated. It is also possible to use higher proportions of isocyanates. Taking this into account, for example 1.0 vs.
1.55 to 1.0 to 1.6 are possible as upper molar ratios.
The lower the proportion of isocyanate, the lower the molecular weight and the lower the viscosity of the polyaddition product. Generally, it is preferred that the molar ratio of alkanolamine to organic polyisocyanate is from 1.0:0.8 to 1.0:1.1.

If a crosslinking reaction inhibitor is added that limits the crosslinking reaction and therefore suppresses gelation, the above upper limit molar ratio is achieved.
It is even possible to actually exceed 1.0 vs. 1.6. Therefore, although it is usually advantageous to use reaction conditions that give rise to a difunctional reaction of isocyanate and alkanolamine, in some cases and when some alkanolamines, especially triethanolamine, are used, employed reaction conditions that resulted in a trifunctional reaction of the isocyanate and the alkanolamine so that there were virtually no free hydroxy groups that would undesirably interfere with the subsequent polyurethane-forming reaction using the polymer-modified polyol. Eggplant is preferred. In this latter case, it may be desirable to have a molar ratio of alkanolamine to isocyanate of up to, for example, 1.0 to 2.1 or more, and a crosslinking inhibitor (e.g. N-dimethylethanolamine) may be added (e.g. Crosslinking can be limited (with an alkanolamine to crosslinking inhibitor ratio of 1.0 to 1.2).

The concentration of reacted alkanolamine and isocyanate in the polyether polyol and thus of the polyaddition product can vary within a wide range, but is generally between 1 and 35% by weight, preferably 3% by weight.
It should be between 30% and 30% by weight. If a specific concentration of the polyaddition product is required (e.g. for use in the production of polyurethane foams with certain optimum properties, approximately 10% by weight)
(required to achieve the desired concentration), the reactant may be suitably selected directly to the desired concentration, or the polyadduct formed may then be treated with additional polyether as appropriate. It can be diluted with polyol to achieve the desired concentration.

Generally, the mixing of the reactants can be carried out at temperatures above or below their melting points from 0°C to 150°C. Mixing of reactants at room temperature or at 70°C
Preferably, it is carried out at or below its melting point temperature. It is also possible to mix the reaction bodies at temperatures below their melting points.

The reaction is exothermic and an increase in temperature is observed depending on the proportion of polyaddition product formed based on the weight of the polyether polyol.

When mixing the reactive materials, mixing can be carried out more effectively if the particle size of the material to be dispersed is fine (in the case of preparing a dispersion) and the viscosity is low. Using a simple batch process, both reactants, the alkanolamine and one of the polyisocyanates, are first completely dissolved or dispersed in the polyether polyol, and then the reactants are added to a zone under maximum agitation. Although the other can be added, an in-pipe mixing method of these materials can also be used.
In this latter case, i.e., in-line mixing, all of the reactants can be pumped in controlled proportions and mixed simultaneously, or one reactant can be mixed first with the polyether polyol. After mixing, the other reaction donor can be added and mixed.

The dispersion of the polyaddition product in the polyether polyol can be used immediately after the reaction is completed, or alternatively it can be used some time after the reaction is completed. For example, the polyether polyol dispersion of the polyaddition product can be metered directly from the pipe mixer in which the polyaddition reaction takes place to the mixing head of a known type of polyurethane production equipment. If the reaction between the polyisocyanate and the alkanolamine is relatively slow, an intermediate storage tank can be placed between the pipe mixer and the mixing head of the polyurethane production equipment to provide additional time for the reaction to complete. .

The polymer-modified polyols of the present invention may contain additives, such as activators, during or after the reaction is complete.
Stabilizers, crosslinkers, water, blowing agents, flame retardants and pigment pastes can be added.

The polyaddition products of the invention can be used in the production of polyurethane foams. If the product is a stable polyol dispersion, that is, a dispersion in which the dispersed material does not settle or at least remains dispersed during mixing with other foam-forming components, The polyaddition products to be dispersed are particularly effective as polymeric fillers in the production of highly elastic, well-processable foams, contributing to strength while simultaneously disrupting the cell walls. fulfill.

When the product is in the form of a polyol solution, it may be suitable for use in forming polymeric materials that have different properties than those obtained using polyol dispersions.

When the polyaddition product is in the form of a stable dispersion, it is generally suitable for processing into flexible polyurethanes, semi-rigid polyurethanes and rigid polyurethanes with improved properties such as increased hardness and is dispersed in polyols. The polyaddition products have the effect of making the cells open-celled so that the high modulus, non-shrinkable foams known in the industry can be produced. Furthermore, these dispersions are suitable, for example, for the production of polyurethane-based elastomers, dressings and coatings.

When using the dispersion in polyurethane production,
Typically, polyurethane foaming processes utilize dispersion polyols, whose properties, in particular their hydroxyl number and functionality, are selected in a known manner depending on the type of polyurethane being produced. For example, for the production of elastomers, polyether polyols that are predominantly linear or difunctional and have a hydroxyl number in the range of 30 to 170 are preferred. For the production of foams, polyether polyols are selected in a known manner that give soft, semi-rigid or rigid foams. Therefore, for the production of flexible foams, the hydroxyl number should be in the range of 20 to 80 and 2 per molecule.
Polyether polyols having 4 to 4 hydroxy groups, such as ICI polyol PBA1233 (trade name), are preferred. Mixtures of polyether polyols can be used if desired.

The organic polyisocyanates that can be used for polyurethane production are described in the known literature and can be the same organic polyisocyanates already mentioned for reaction with alkanolamines.

The polyurethane foaming reaction mixture can also contain customary components other than the reaction mixture described above, depending on the type of polyurethane being produced. The reaction mixture as a whole therefore contains catalysts such as tertiary amines and organotin compounds, crosslinkers or chain lengthening agents such as diethanolamine, triethanolamine, ethylene glycol, glycerol, dipropylene glycol and phenylene diamine, flame retardants such as It may contain halogenated alkyl phosphates as well as fillers such as barium sulfate.

For foam production, a blowing agent is included in the reaction mixture. Examples of suitable blowing agents include water, which reacts with the polyisocyanate to generate carbon dioxide, as well as water, which evaporates under the influence of an exothermic reaction.
or, when using a mechanical foaming process, a blowing agent that includes an inert volatile liquid that evaporates upon release of pressure. An example of this type of liquid, which is the latter blowing agent, is preferably a liquid with a boiling point not exceeding 100°C at atmospheric pressure.
Halogenated hydrocarbons, in particular chlorinated hydrocarbons such as trichlorofluoromethane and dichlorodifluoromethane, and chlorinated hydrocarbons such as dichloromethane. The amount of blowing agent is selected in known manner to provide a foam of the desired density. In general, amounts providing 0.005 to 0.3 moles of gas per 100 g of reaction mixture will be suitable. If necessary, it can be produced by overfilling, i.e. by foaming the reaction mixture in a closed mold with a volume smaller than the volume that would be occupied by the foam obtained if the reaction mixture were allowed to foam freely without restraint. The density of the foam can be varied.

Generally, the composition of the polyurethane-forming reaction mixture should be such that the ratio of isocyanate groups to active hydrogen atoms is substantially within the range of 0.9:1 to 1.2:1, although higher ratios may be used if necessary. You can also do it.

When producing polyurethane foams, foam stabilizers such as polysiloxane-polyalkylene oxide block copolymers optionally including direct carbon-silicon or carbon-oxygen-silicon bonds between the organic unit and the polysiloxane unit are used. Alternatively, it is usually necessary to stabilize or condition the cells formed by the addition of cell conditioners. When attempting to produce "high modulus" polyurethane,
Dimethyl silicone oil or a low molecular weight agent containing it, such as silicone manufactured by Theodore Goldschmidt AG.
It is appropriate to add B8616 (trade name).

One shot, prepolymer or quasi prepolymer methods may be employed as appropriate for the particular type of polyurethane being produced.

The components of the polyurethane-forming reaction mixture can be mixed together in any conventional manner, for example using any mixing equipment for this purpose described in the prior art literature. If desired, some of the individual components can be premixed to reduce the number of component streams that need to be brought together in the final mixing step. It is often advantageous to have a two stream system, one stream being the polyisocyanate or prepolymer stream and the second stream containing all the other reaction mixtures.

The invention is further illustrated, but by no means by way of limitation, by the following examples. Parts and percentages used in examples
All are parts and percentages by weight.

The meanings of the abbreviations used with respect to polyether in each example are as follows.

Polyether A A polyether of propylene oxide starting from glycerol and treated with 15% ethylene oxide to give a hydroxyl number of 35 and a primary hydroxy group content of about 75%.

Polyether B Starting from trimethylolpropane, it is treated with ethylene oxide to reduce the OH number to 34 and to primary OH
Polyether of propylene oxide with a group content of approximately 80%.

Polyether C A polyether of propylene oxide starting from glycerol and increasing the OH number to 47 and the primary OH group content to 5% or less using ethylene oxide.

Polyether D A linear polypropylene glycol containing secondary hydroxyl groups and having an OH number of 56.

Example 1 900 g of polyether A at a temperature of 20 °C are mixed with 48.7 g of triethanolamine at a temperature of 20 °C under high-speed mixing conditions, followed by 80% of 2,4-tolylene diisocyanate and 20% of 2,6-tolylene diisocyanate. 51.2 g of the mixture was added over 5 minutes. Then dibutyl-tin-dilaurate catalyst
When 0.3 g was added, a rapid reaction occurred and the temperature of the mixture increased to 20 °C within a period of 3 minutes after the catalyst addition was complete.
The temperature rose from 37℃ to 37℃.

A stable dispersion of 10% solids obtained upon cooling had a viscosity of 1600 centipoise at 25°C.

Pour 300 g of the above product into a beaker, then add 7.8 g of water, 3 g of diethanolamine, and 0.21 g of bis(2-dimethylaminoethyl) ether.
"Silicone B8616" manufactured by Goldschmidt
(trade name) was added, the temperature was adjusted to 22°C, and the mixture was stirred. Next, dibutyl-tin-dilaurate
After 0.75 g was added, 117 g of a mixture of 80% 2,4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate was added and stirred for 10 seconds. After an additional 5 seconds, the mixture was poured into the box and foaming began.

After an additional 105 seconds from the end of mixing, a non-shrinkable "high modulus" foam was produced with the following properties:

Density Kg/m ³ 34 CLDg/cm ² (1) 28 Repulsion % (2) 63 (1): Resistance to compression at strain rate of 40% (2): Ball repulsion example 2 920 g of polyether A at 20°C is placed in a beaker and then 32.1 g of diethanolamine at 30° C. was added at room temperature with mechanical stirring. 80% 2,4-tolylene diisocyanate and 20% 2,
47.9g mixture with 6-tolylene diisocyanate
was added over a period of 30 seconds into the stirring vortex of the above mixture. A white stable dispersion is formed and the temperature decreases from 20°C within 30 seconds after the isocyanate addition is complete.
The temperature rose to 37℃. The polyadduct contains isocyanate and alkanolamine in a molar ratio of 0.9 to 1.0, and the final product contains 8.0% polyadduct in polyether polyol and is acceptable at ambient temperature. It had a reasonable viscosity.

Collect 300 g of the above product into a beaker, then add 7.8 g of water, 3 g of diethanolamine, and 0.21 g of bis(2-dimethylaminoethyl) ether.
“Silicone B8616” manufactured by Goldschmidt
(trade name) was added thereto, the temperature was adjusted to 22°C, and the mixture was stirred. Next, dibutyl-tin-dilaurate
0.75g was added, stirred for 10 seconds, then 80%
2,4-tolylene diisocyanate and 20% 2,6
-117 g of a mixture with tolylene diisocyanate were added. After an additional 5 seconds, the mixture was poured into the box and foaming began. After a further 105 seconds from the end of mixing, a non-shrinkable "high elastic" product with similar properties to those in Example 1 is produced.
form was manufactured.

Example 3 A foam was prepared according to the method described in Example 2, except that 300 g of polyether polyol containing polyaddition product was replaced by 300 g of polyether polyol and only 100 g of isocyanate was used. Foaming to produce the foam occurred as in Example 2, but the resulting foam shrank and its properties were not measurable.

Example 4 A dispersion containing a polyaddition product in a polyether polyol is prepared using polyether A according to the method described in Example 2, which dispersion contains tin octoate instead of dibutyl-tin-dilaurate.
The foaming process was carried out according to the method described in Example 2, except that 0.6 g was used. A highly elastic, non-shrinkable foam with properties similar to those obtained by the method described in Example 1 was obtained.

Example 5 A polyaddition product was prepared and subjected to a foaming process as described in Example 2, except that polyether A was replaced by polyether B. The stable dispersion in polyether polyol had a solids content of 8% and an acceptable viscosity at ambient temperature. The resulting foam was non-shrinkable and had properties similar to the foam of Example 1.

Example 6 A dispersion containing the polyaddition product in polyether was prepared by the method described in Example 2, with the exception that the molar ratio of isocyanate to alkanolamine was 1.1 to 1.0, the solids content being 8%. was maintained. The resulting product had a high viscosity of over 2500 centipoise at 25°C, but was usable. When foamed according to the method described in Example 2, a highly elastic, non-shrinkable foam was obtained.

Example 7 Polyether A was prepared by the method described in Example 2 except that the molar ratio of isocyanate to alkanolamine was 0.45 to 1.0 and the total solids content was 8%.
A dispersion containing the polyaddition product therein was produced. When foaming was performed by the method described in Example 2,
A contractile foam was obtained. Properties of this form could not be measured.

Example 8 920g of polyether A at a temperature of 20°C was taken and mixed with 24.5g of diethanolamine at a temperature of 30°C, and then mixed with 55.5g of crude MDI with vigorous stirring. A dispersion containing the polyaddition product in a polyether polyol was obtained, which had a solids content of 8% and was usable, but had a high viscosity of over 3000 centipoise at 25°C. was.

This product was foamed according to the method described in Example 2 to yield a highly elastic, non-shrinkable foam.

Example 9 800 g of polyether C was collected, 80.24 g of diethanolamine was added at a temperature of 30°C, and while mixing, 80% 2,4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate were mixed. A stable dispersion based on polyether C at a temperature of 20° C. was produced by adding 119.75 g of the mixture over a period of 1 minute. A temperature increase to 29° C. was observed and after cooling the product had an acceptable viscosity at ambient temperature and a solids content of 20%.

Example 10 A stable dispersion was prepared by the method described in Example 9, except that Polyether C was replaced by Polyether D. The resulting polyaddition compound based on polyether D had a solids content of 20% and an acceptable viscosity at ambient temperature.

The stable dispersions prepared by the methods described in Examples 1, 2 and 5-10 were nonionic. That is, these dispersions contain covalent polymeric materials devoid of ionic groups. Furthermore, virtually no water or other ionic medium is used or present in the dispersion during the preparation of the dispersion. In connection with this latter point, namely the absence of water or other ionic media in the dispersion, there is a tendency for commercially available polyols and other starting materials to contain trace amounts of water. Although this level of moisture is acceptable, the presence of water is generally undesirable and the moisture content must be maintained at the lowest possible level. The moisture content is desirably not more than 1% by weight, more preferably not more than this value, for example 0.1% by weight or less, but the method of the present invention can be used in some cases even if the moisture content is more than 1% by weight. Please note that this is possible.

The polyols used in carrying out the method of the invention are:
In particular when used as starting materials for the formation of polyurethane foams, they can be of the triol type containing predominantly primary hydroxyl groups. However, in the production of polymer-modified polyols by the process of the invention, in particular in the production of dispersions such as those described in the examples above, all or most of the isocyanate reacts with the olamine and all or most of the polyol remains unreacted. It will be appreciated that it is possible to use any suitable polyol, which acts as a carrier and is specifically chosen depending on the requirements of the subsequent polyurethane-forming reaction in which the polymer-modified polyol is used. Thus, for example, polyols which are triols and/or diols having primary and/or secondary hydroxyl groups or polyols having other suitable structures can be used.

Claims (1)

[Scope of Claims] 1. A method for producing polyurethane comprising reacting a polymer-modified polyol previously produced by polymerization of an alkanolamine and an organic polyisocyanate with an isocyanate in the presence of a polyol, wherein the alkanolamine is By reacting with the isocyanate in a molar ratio of 1.0/0.5 to 1.0/1.6, the alkanolamine is at least predominantly polyfunctionally reacted with the isocyanate and the polyol is free from any unused substances during the pre-production of the polymer-modified polyol. A method characterized in that it acts at least predominantly as a reaction carrier. 2. In the presence of a polyether polyol with a molecular weight in the range of 200 to 10,000, the alkanolamine and isocyanate are mixed in a ratio of about 1.0/0.5 to 1.0/
Process according to claim 1, characterized in that the reacted alkanolamine and polyisocyanate are mixed in a molar ratio of 1.6 and together account for 1 to 35% by weight based on the weight of the polyol. . 3 Alkanolamine with isocyanate 1/
The method according to claim 1, characterized in that the reaction is carried out in a molar ratio of 0.8 to 1/1.1. 4. The production method according to any one of claims 1 to 3, wherein the alkanolamine is triethanolamine. 5. A method for producing polyurethane comprising reacting a polymer-modified polyol previously produced by polymerization of an alkanolamine and an organic polyisocyanate with an isocyanate in the presence of a polyol, wherein the alkanolamine is reacted with an isocyanate in the presence of a crosslinking reaction inhibitor. with the isocyanate and 1.0/
By reacting at a molar ratio greater than 1.6, the alkanolamine reacts at least predominantly polyfunctionally with the isocyanate and the polyol is at least predominantly present as an unreacted carrier during the pre-production of the polymer-modified polyol. A method characterized by acting. 6. The production method according to claim 5, wherein the alkanolamine is triethanolamine. 7. A method for producing polyurethane comprising reacting an isocyanate with a polymer-modified polyol previously produced by polymerization of an alkanolamine and an organic polyisocyanate in the presence of a polyol, wherein the alkanolamine is reacted with the isocyanate in a ratio of 1.0/0.5 to By reacting in a molar ratio of 1.0/1.6, the alkanolamine is at least predominantly polyfunctionally reacted with the isocyanate, and the total amount of alkanolamine and polyisocyanate is equal to or less than the weight of the polyol, based on the weight of the polyol. The amount is 10% by weight or more on a standard basis, and the polyol acts at least predominantly as an unreacted carrier when a polyol is further added after the polymerization of the isocyanate and the alkanolamine to produce a polymer-modified polyol. Method. 8. The production method according to claim 7, wherein the alkanolamine is triethanolamine. 9. A method for producing polyurethane comprising reacting an isocyanate with a polymer-modified polyol previously produced by polymerization of an alkanolamine and an organic polyisocyanate in the presence of a polyol, in which the polymerization reaction between the alkanolamine and the polyisocyanate is promoted. and reacting the alkanolamine with the isocyanate in a molar ratio of 1.0/0.5 to 1.0/1.6, such that the alkanolamine is at least predominantly polyfunctionally reacted with the isocyanate and the polyol is A process characterized in that it acts at least predominantly as an unreacted carrier during the preproduction of polymer-modified polyols. 10. Process according to claim 9, characterized in that the catalyst is selected from organometallic compounds and amines. 11. A method for producing polyurethane comprising reacting an isocyanate with a polymer-modified polyol previously produced by polymerizing an alkanolamine and an organic polyisocyanate in the presence of a polyol, in which the polymerization reaction between the alkanolamine and the polyisocyanate is adjusted. and reacting the alkanolamine with the isocyanate in a molar ratio of 1.0/0.5 to 1.0/1.6, so that the alkanolamine reacts at least predominantly polyfunctionally with the isocyanate;
and the polyol acts at least predominantly as an unreacted carrier during the preproduction of the polymer-modified polyol. 12. Process according to claim 11, characterized in that the reaction regulating additive is selected from monofunctional isocyanates, monofunctional amines and dialkylalkanolamines. 13. Process according to claim 1, characterized in that the isocyanate reacting with the polyol is the same as the isocyanate used in the production of the polymer-modified polyol. 14. A method for producing polyurethane comprising reacting an isocyanate with a polymer-modified polyol previously produced by polymerization of an alkanolamine and an organic polyisocyanate in the presence of a polyol, wherein the alkanolamine is mixed with the isocyanate in a ratio of 1.0/0.5 to By reacting in a molar ratio of 1.0/1.6, the alkanolamine is at least predominantly polyfunctionally reacted with the isocyanate and the polyol is at least predominantly as an unreacted carrier during the pre-production of the polymer-modified polyol. and in the presence of additives selected from blowing agents, catalysts, stabilizers, crosslinking agents, flame retardants, pigments, fillers, the polyol reacts with isocyanates to produce polyurethanes. Method.