WO2013156237A2

WO2013156237A2 - Compounds having guanidine groups and use thereof as additives in the production of polyurethane systems

Info

Publication number: WO2013156237A2
Application number: PCT/EP2013/055601
Authority: WO
Inventors: Eva Emmrich-Smolczyk; Mladen Vidakovic; Michael Ferenz; Martin Glos
Original assignee: Evonik Industries Ag
Priority date: 2012-04-16
Filing date: 2013-03-19
Publication date: 2013-10-24
Also published as: WO2013156237A3; DE102012206193A1

Abstract

The invention relates to aminofunctional polymers having guanidine groups, the production thereof and the use thereof for producing polyurethane systems and correspondingly produced polyurethane systems.

Description

E V O N I K i n d u s t r i e s A G, Essen

Guanidinruppen containing compounds and their use as additives in the production of polyurethane systems.

The invention relates to aminofunctional polymer compounds having guanidine groups, their preparation and their use for the preparation of polyurethane systems and polyurethane systems prepared accordingly. Polyurethane systems are z. Polyurethane coatings, polyurethane adhesives, polyurethane sealants, polyurethane elastomers or polyurethane foams / foams.

Polyurethane foams are used in a wide variety of applications due to their excellent mechanical and physical properties. A particularly important market for various types of polyurethane foams, such as conventional ether and ester polyol based flexible foams, cold foams (often referred to as HR foams), rigid foams, integral foams and microcellular foams, as well as foams whose properties lie between these classifications, such as , B. semi-rigid systems, represents the automotive and furniture industry. B. rigid foams as a headliner, ester foams for the interior lining of the doors and for punched sun visors, cold and soft foams used for seating systems and mattresses.

The problem with the production and storage of polyurethane foams is the release of aldehydes, in particular formaldehyde. In the US and Europe, the foam manufacturers have launched a voluntary program "CertiPUR", which is a standard

Limit on formaldehyde emissions of 0.1 mg / m ³ as measured by ASTM Method D5116-97 "Small Chamber Test" when conditioned for 16 hours. The European chamber test allows 5 μg / L of formaldehyde and DMF in fresh foams and 3 μg / L in foams older than 5 days.

According to WO 2009/117479, the formaldehyde should originate from the raw materials and should be present in particular in the amine catalysts (tertiary amines) used. To achieve low formaldehyde emissions, this document proposes to add a primary amine to the tertiary Armin catalyst. This primary amine may, for. B. also be a guanidine. US Pat. No. 6,040,315A describes the preparation of guanidine group-containing copolymers by copolymerization of amino-functional polymers and guanidine carbonate, the reaction being carried out with a guanidine carbonate to give amino-functional polymers of greater than 5: 4. The copolymers are described as gastric acid deacidifying agents.

EP 0915083 A2 describes the preparation of substituted guanidine derivatives which, for. B. as sterically hindered bases, biocides and complex ligands are known in which an alkylated isourea is reacted with a primary or secondary amine. In the context of the present invention, it has been observed that the emissions of formaldehyde frequently increase with increasing storage of a polyurethane foam.

The object of the present invention was therefore to provide an additive which prevents the emission of formaldehyde over a relatively long period of time or to which it reduces the abovementioned limits to a limited extent.

Surprisingly, it has been found that amino-functional polymer compounds of the below-mentioned formula (Ia), in particular guanidine-containing amino-functional polymer compounds of the formula (I) below, achieve this object.

The present invention therefore relates to compounds of the formula (I) as defined below and in claim 1. Likewise provided by the present invention is a process for the preparation of compounds of the formula (I) and the use of compounds of the formula (I) in the preparation of polyurethane systems and corresponding polyurethane systems themselves.

The compounds of the formula (I) according to the invention have the advantage that, when used as an additive in polyurethane foam production, the emission of formaldehyde is also determined after storage for 3 months to a value of 0.02 mg formaldehyde / kg PU foam according to VDA 275 limit.

The compounds according to the invention, a process for their preparation, the use of the compounds for the preparation of the polyurethane system or foams and the polyurethane system or foams themselves are described below by way of example, without the invention being restricted to these exemplary embodiments. are hereinafter ranges, general formulas or classes of compounds are meant to include not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by extracting individual values (ranges) or compounds can. If documents are cited in the context of the present description, their content, in particular with regard to the matters referred to, should form part of the disclosure content of the present invention. If the following information is given as a percentage, it is, unless stated otherwise, in% by weight. If mean values are given below, this is the number average, unless otherwise stated. Are below material properties such. As viscosities or the like, it is, unless otherwise stated, the material properties at 25 ° C. In the present invention, when chemical (sum) rolls are used, the indices given may be both absolute numbers and averages, and for polymeric compounds, the indices are preferably average values.

The compound according to the invention is characterized in that it has the formula (I)

RcXxX'xYyY (i)

R ¹ ₂ N-CH ₂ -, preferably H ₂ N-CH ₂ -,

-CH NR ^1b -CH, preferably -CH _r NH-CB

NR ⁴ NR ⁴ ₂ NHR ⁴

-NR ⁴ -C ₄ -N = C ₄ - N = q

NR 2 or 2 preferably NHR ⁴

R ¹ = identical or different alkyl radicals, - [CnF OJ _d H, H or -C (O) R ² , preferably alkyl radicals having 1 to 3 carbon atoms or -H, particularly preferably -H, with n = 2, 3 or 4, preferably n = 2 or 3, d = 1 to 20, preferably 1 to 10,

R ^1b = R ¹ or -C (NR ⁴ ₂ ) (NR ⁴ ), preferably R ¹ ,

R ² = identical or different alkyl or aryl radical having 1 to 24 carbon atoms, preferably methyl,

c = 0 or 1, preferably 0

x = 0 to 300, preferably 1 to 90, in particular> 2 to 30,

x '= 2 to 150, preferably 2 to 50, in particular 2 to 25,

y = 0 to 300, preferably 1 to 90, in particular 2 to 30,

y '= 0 to 300, preferably 0.5 to 90, in particular 1 to 30,

x + x '+ y is greater than or equal to 3, preferably greater than or equal to 5,

R ^{4 is} identical or different alkyl or aryl radical, preferably having 3 to 10 carbon atoms, preferably alkyl radicals having 3 to 6 carbon atoms, particularly preferably cyclohexyl or isopropyl radicals, or H, preferably cyclohexyl or isopropyl radicals or H, particularly preferably cyclohexyl or isopropyl radicals,

Z = a + b is a cohesive organic radical, preferably a cyclohexyl radical or a radical - (CH ₂ ) _e - where e = 3, 4, 5 or 6,

a = 0 to 3, preferably 1 or 2,

b = 0 to 3, preferably 0 or 1

a + b is greater than or equal to 1.

Preferably, x + x '+ y + y' is greater than or equal to 3. Preferably, y 'is greater than or equal to 5.

The compounds of the formula (I) preferably have a molecular weight Mn of 400 to 25,000 g / mol.

Particularly preferred compounds of the formula (I) are those in which all the radicals R are either cyclohexyl or isopropyl radicals or H.

The compounds of formula (I) according to the invention are e.g. thereby obtainable or can be obtained by reacting a compound of the formula (III)

RaXxYyV (III) with R, X, Y, a, x, y and y 'as defined for formula (I) and with the proviso that x

is equal to 3, preferably greater than or equal to 5, with a compound of the formula (IV)

R ⁴ -N = C = NR ⁴ with R ⁴ as defined for formula (I), preferably cyclohexyl or isopropyl radicals,

is reacted, wherein the molar ratio of the compounds of formulas (III) to

Compounds of formula (IV) is at least 1 to 2, preferably 1 to 2 to 1 to 20, preferably 1 to 5 to 1 to 10. Accordingly, the process according to the invention for the preparation of compounds of the formula (I) is characterized in that a compound of the formula (III)

RaXxY _y (IN) with R, X, Y, Y, a, x, y and y 'as defined for formula (I) and the proviso that x + y is greater than or equal to 3, preferably greater than or equal to 5, with a compound of the formula (IV)

R ⁴ -N = C = NR ⁴ (IV) with R ⁴ as defined for formula (I), preferably cyclohexyl or isopropyl radicals,

is reacted, wherein the molar ratio of the compounds of formulas (III) to

Compounds of formula (IV) is at least 1 to 2, preferably 1 to 2 to 1 to 20, preferably 1 to 5 to 1 to 10.

Compounds of the formula (Ia)

RcXxX'xYyYy (la) with

XR ¹ ₂ N-CH ₂ -, preferably H 2N-CH 2 -,

X'G-CHΙ; 2-,

Y is -CH 2 -NR-CH 2 -, preferably -CH NH-CH,

CH ₂ -N-CH ₂ -

CH;

Y

R ¹ = identical or different alkyl radicals, - [C _n H OJ _d H, H or -C (O) R ² , preferably alkyl radicals having 1 to 3 carbon atoms or -H, particularly preferably -H, with n = 2, 3 or 4, preferably n = 2 or 3, d = 1 to 20, preferably 1 to 10,

R ^1b = R ¹ or C (NR ⁴ ₂ ) (NR ⁴ ), preferably R ¹ ,

c = 0 or 1, preferably 0

x = 0 to 300, preferably 1 to 90, in particular> 2 to 30

x '= 0 to 150, preferably 0 to 50, in particular 2 to 25,

y = 0 to 300, preferably 1 to 90, in particular 2 to 30,

y '= 0 to 300, preferably 0.5 to 90, in particular 1 to 30,

a = 0 to 3, preferably 1 or 2,

b = 0 to 3, preferably 0 or 1, and

a + b is greater than or equal to 1,

can be used according to the invention in the preparation of a polyurethane system, in particular a polyurethane foam, preferably as an additive, in particular as an additive for the prevention or reduction of formaldehyde emissions. The compound of the formula (Ia) used is preferably a compound of the formula (I) as described above. In this use, the compounds of formula (Ia) are preferably a reaction mixture containing one or more organic isocyanates having two or more Isocyanate functions, one or more polyols having two or more isocyanate-reactive groups, catalysts for the reactions isocyanate-polyol and / or isocyanate-water and / or the isocyanate trimerization, water, optionally physical blowing agents, optionally flame retardants and optionally further Additive added.

Preferably, the amount of compounds of the formula (Ia) added to the reaction mixture is from 0.1 to 10 parts by mass of compounds of the formula (Ia) per 100 parts by mass of polyols. The preparation of the polyurethane system, in particular of the polyurethane foam, in which one or more compounds of the formula (Ia) is used according to the invention can be carried out in a manner known to the person skilled in the art. A basic overview can be found z. In G. Oertel, Polyurethane Handbook, 2nd edition, Hanser / Gardner Publications Inc., Cincinnati, Ohio, 1994, p. 177-247.

As isocyanate component, all isocyanates, in particular the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates known per se, may be present in the reaction mixture. Suitable isocyanates in the sense of this invention are preferably all polyfunctional organic isocyanates, such as ^{4,4'-diphenylmethane} diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI). Particularly suitable is the mixture known as "polymeric MDI"("crudeMDI") of MDI and higher condensed analogues having an average functionality of 2 to 4, and the various isomers of TDI in pure form or as a mixture of isomers. Particularly preferred isocyanates are mixtures of TDI and MDI.

Suitable polyols for the purposes of this invention are preferably all organic substances having a plurality of isocyanate-reactive groups, as well as their preparations. Preferred polyols are all polyether polyols and polyester polyols customarily used for the preparation of polyurethane systems, in particular polyurethane foams.

The polyols are preferably not compounds having at least one 5- or 6-membered ring composed of one or two oxygen atoms and carbon atoms. Polyether polyols are obtained by reacting polyhydric alcohols or amines with alkylene oxides. Polyester polyols are based on esters of polybasic carboxylic acids (which may be either aliphatic, for example adipic acid, or aromatic, for example phthalic acid or terephthalic acid) with polyhydric alcohols (usually glycols). In addition, natural oils based on natural oils (natural oil based polyols, NOPs) can be used. These polyols are derived from natural oils such as soy or palm oil and can be used unmodified or modified.

A suitable ratio of isocyanate to polyol, expressed as the index of the additive composition, is in the range of 10 to 1000, preferably 40 to 350. This index describes the ratio of actually used isocyanate to isocyanate (calculated for a stoichiometric reaction with polyol). An index of 100 indicates a molar ratio of the reactive groups of 1 to 1.

Suitable further catalysts which may additionally be present in the additive composition according to the invention are substances which catalyze the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) or the di- or trimerization of the isocyanate. Typical examples are amines, e.g. Triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1, 2-dimethylimidazole, N-ethylmorpholine, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, dimethylaminoethanol, dimethylaminoethoxyethanol and bis (dimethylaminoethyl) ether, Tin compounds such as dibutyltin dilaurate and potassium salts such as potassium acetate. Preferably used as further catalysts are those which contain no organic tin compounds, in particular no dibutyltin dilaurate. Suitable amounts of these catalysts depend on the type of catalyst and are usually in the range of 0.01 to 5 pphp (= parts by weight based on 100 parts by weight of polyol) or 0.1 to 10 pphp for potassium salts.

Suitable water contents in the additive compositions according to the invention depend on whether or not physical blowing agents are used in addition to the water. In the case of pure water-driven foams, the values are typically from 1 to 20 pphp, if other blowing agents are additionally used, the amount of use is reduced to usually 0 or 0.1 to 5 pphp. To obtain high foam chamber weights, neither water nor other blowing agents are used. Suitable physical blowing agents for the purposes of this invention are gases, for example liquefied C0 ₂ , and volatile liquids, for example hydrocarbons having 4 or 5 carbon atoms, preferably cyclo, iso and n-pentane, hydrofluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferably HCFC 141b, oxygen-containing compounds such as methyl formate and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1, 2-dichloroethane. Furthermore, ketones (eg acetone) or aldehydes (eg methylal) are suitable as blowing agents.

In addition to or instead of water and optionally physical blowing agents, other chemical blowing agents which react with isocyanates to evolve gas, such as formic acid or carbonates may be present in the additive composition according to the invention.

Suitable flame retardants in the context of this invention are preferably liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. Triethyl phosphate (TEP), halogenated phosphates, e.g. Tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. Dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus. Furthermore, halogenated compounds, for example halogenated polyols, and solids such as expanded graphite and melamine are suitable as flame retardants.

By the use according to the invention of the compounds according to the invention, corresponding polyurethane systems can be prepared. The compounds of the formula (I) according to the invention can in principle be used in all processes for the preparation of

Polyurethane systems are used. The term polyurethane is used here as a generic term for a diisocyanate or polyisocyanates and polyols or other isocyanate-reactive species, such as. Amines to understand produced polymer, wherein the urethane bond does not have to be exclusive or predominant type of bond. Also, polyisocyanurates and polyureas are expressly included.

The use of the compounds of the formula (Ia), preferably of the compounds of the formula (I) according to the invention for the preparation of polyurethane systems, in particular polyurethane foams or the preparation of the polyurethane systems / polyurethane foams can be carried out by all methods familiar to the skilled worker, for example by hand mixing or preferably with the aid of from High pressure or low pressure foaming machines. The process according to the invention can be carried out continuously or batchwise. A discontinuous implementation of the method is preferred in the production of molded foams, refrigerators or panels. Continuous process control is preferred in the manufacture of insulation boards, metal composite elements, blocks or spraying processes.

In the process according to the invention, the compounds according to the invention are preferably mixed together directly before or else only during the reaction (to form the urethane bonds). Preferably, the combination / addition of the compound takes place in a mixing head.

The polyurethane systems according to the invention are characterized in that they contain from 0.05 to 10% by mass, preferably from 0.1 to 5% by mass, based on the total composition of the polyurethane system, of compounds of the formula (Ia), preferably compounds of the formula (I ) exhibit.

The polyurethane systems of the invention may preferably z. As a rigid polyurethane foam, a flexible polyurethane foam, a viscoelastic foam, an HR foam, a semi-rigid polyurethane foam, a thermoformable ble polyurethane foam or an integral foam, preferably a polyurethane HR foam.

The polyurethane systems of the invention, preferably polyurethane foams, z. As refrigerator insulation, insulation board, sandwich element, pipe insulation, spray foam, 1- & 1, 5-component foam foam, imitation wood, model foam, packaging foam, mattress, furniture upholstery, automotive seat cushion, headrest, instrument panel, automotive

Interior trim, automobile headliner, sound absorbing material, steering wheel, shoe sole, carpet back foam, filter foam, sealant, sealants and adhesives, or to be used to make such products. In the examples given below, the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples. Examples:

Used raw materials: Sigma-Aldrich was used to obtain N, N-dicyclohexylcarbodiimides (order number D80002) and two aqueous solutions of amino-functional polymers of general formula 1 (amino-functional polymer A (order number: 482595) and amino-functional polymer B (order number 408700) Both amino-functional polymers were dried by distillation so far that the water content was <1% by mass.

Preparation of additive 1

61 g of the amino-functional polymer A were initially charged in a 250 ml three-necked flask with KPG stirrer and admixed with 41 g of N, N-dicyclohexylcarbodiimide. This mixture was heated to 90 ° C and stirred for six hours. Subsequently, the volatile constituents were removed by distillation at 20 mbar and 90.degree. Preparation of additive 2

59 g of the amino-functional polymer B were initially charged in a 250 ml three-necked flask with KPG stirrer and admixed with 44 g of N, N-dicyclohexylcarbodiimide. This mixture was heated to 90 ° C and stirred for six hours. Subsequently, the volatile constituents were removed by distillation at 20 mbar and 90.degree.

Additive 3

3- (Dimethylamino) -1-propylamine was ordered from Sigma-Aldrich (order number D145009) and used as is. Preparation of additive 4

27 g of 3- (dimethylamino) -1-propylamine (see additive 3) were placed in a 250 ml three-necked flask with KPG stirrer and admixed with 53 g of N, N-dicyclohexylcarbodiimide. This mixture was heated to 90 ° C and stirred for six hours. Subsequently, the volatile constituents were removed by distillation at 20 mbar and 90.degree.

Additive 5

Guanidine carbonate (CAS: 593-85-1) was purchased from Sigma-Aldrich (order number G1 1659) and used as received.

Table 1: Raw materials for the production of foam moldings Polyetherol trifunctional, MW 6000, Bayer MaterialScience

Polyol 1 AG

Polyol 2 Polyetherol Trifunctional, MW 4500, Dow Chemicals

Tegoamine DEOA 85 (diethanolamine 85% in water),

Crosslinker Evonik Industries AG

Tegoamine ZE1 (1, 1 '- {[3-

(dimethylamino) propyl] imino} bispropan-2-ol), Evonik

Catalyst Industries AG

Silicone stabilizer Tegostab B 8734 LF 2, Evonik Industries AG

Methylene diisocyanate, Suprasec 6506, NCO = 29.3%,

Isocyanate Huntsman

The amounts of additive used were chosen so that the sum of the amounts of primary amine, secondary amine and guanidine functions in the test formulation was constant. For this purpose, the amine number based on the sum of primary amine, secondary amine and guanidine functionalities of the additive was estimated on the basis of the available structural information (Table 2).

Table 2: Amine numbers and initial weight of additive

Example 1 Production of Polyurethane Foams

The foaming was carried out by hand mixing. For this purpose, polyol, crosslinker, catalyst, additive, water and silicone stabilizer were weighed into a beaker and premixed with a paddle stirrer for 60 s at 1000 rpm. Subsequently, the isocyanate was added and stirred at a stirrer speed of 2500 rpm 7s. The reaction mixture was sealed in a box mold heated to 57 ° C. (dimensions 40 × 40 × 10 cm). The finished foam was removed from the mold after 3.5 minutes. The amounts used and reactants can be found in Table 3.

The molded foams produced by the process described above were then modeled after the VDA 275 (VDA 275 "Moldings for the vehicle interior - determination of formaldehyde release." Measuring method according to the modified bottle method; Source: VDA 275, 07/1994, www.vda .de) analyzed for their formaldehyde content, which is explained below. measuring principle

In the method, specimens of a given mass and dimension were fixed over distilled water in a closed 11-glass bottle and stored at a constant temperature for a defined time. Thereafter, the bottles were cooled and determined in distilled water, the absorbed formaldehyde. The determined amount of formaldehyde was based on dry molding weight (mg / kg).

analytics

Specimens: Sample preparation, sampling and specimen dimensions

After demolding the foams, they were stored for 24 hours at 21 ° C and about 50% relative humidity. Test specimens were then uniformly distributed across the width of the (cooled) molding at appropriate and representative locations. Thereafter, the foams were wrapped in an aluminum foil and sealed in a polyethylene bag.

The size of the specimens was 100x40x40mm thickness (about 9g). Per specimen 3 specimens were removed for the determination of formaldehyde.

Performance of the test: Formaldehyde release

Immediately after receipt of the sealed specimens they were fed to the direct determination. The samples were weighed to the nearest 0,001g before analysis on the analytical balance. 50 ml of distilled water were pipetted into each of the glass bottles used. After attaching the specimens in the glass bottle, the vessel was closed and kept for 3 hours in a warming cabinet at a constant temperature of 60 ° C. After the test period, the vessels were removed from the oven. After 60 minutes of service life at room temperature, the test specimens were removed from the test bottle. Subsequently, the derivatization was carried out according to the DNPH method (dinitrophenylhydrazine). To 900 μΙ of the water phase with 100μΙ of a DNPH solution are added. The DNPH solution is prepared as follows: 50mg DNPH in 40mL MeCN (acetonitrile) is acidified with 250μί HCl (1:10 dil) and made up to 50mL with MeCN. Device parameters HPLC

The following device was used for the analysis:

Agilent Technologies 1260

Chromatography column: Phenomenex Luna 250 ^* 4, 6mm C18, 5μ particle size

Eluent: water acetonitrile gradient

Detection: UV 365 nm

The results of the test can be found in Table 3. Table 3: Formulation for the production of the moldings and results of the formaldehyde measurements

The foaming results show that when additives 1 and 2 are added, the formaldehyde content is close to the blank value, i. there is almost no measurable formaldehyde emission detectable. On the other hand, when additive 3 or 5 is added, there is no positive effect in the form of a reduction in the formaldehyde emissions that occur. However, the modification of the additive 3, from which the additive 4 results, shows a - albeit not so pronounced effect on the formaldehyde emissions.

Conclusion:

The foaming results show that PU foams having reduced formaldehyde emissions can be produced by adding the additives according to the invention.

Claims

claims:

1. Compound of formula (I)

RcXxX 'Yy' y (i) with

XR ¹ ₂ N-CH _:

X'G-CH

Y -CH ₂ -NR -CH T

R ¹ = identical or different alkyl radicals, - [CnH OJ _d H, H or -C (O) R ² , preferably alkyl radicals having 1 to 3 carbon atoms or -H, particularly preferably -H, with n = 2, 3 or 4, preferably n = 2 or 3, d = 1 to 20, preferably 1 to 10,

R ^1b = R ¹ or C (NR ⁴ ₂ ) (NR ⁴ ), preferably R ¹ ,

c = 0 or 1, preferably 0

x = 0 to 300, preferably 1 to 90, in particular> 2 to 30,

x '= 2 to 150, preferably 2 to 50, in particular 2 to 25,

y = 0 to 300, preferably 1 to 90, in particular 2 to 30,

y '= 0 to 300, preferably 0.5 to 90, in particular 1 to 30,

R ^{4 is the} same or different alkyl or aryl radical or H, Z = a + b is a cohesive organic radical, preferably a cyclohexyl radical or a radical - (CH ₂ ) _e - where e = 3, 4, 5 or 6,

a = 0 to 3,

b = 0 to 3

a + b is greater than or equal to 1.

2. A compound according to claim 1, characterized in that y 'is greater than or equal to 5.

3. A compound according to claim 1 or 2, characterized in that the compound has a molecular weight Mn of 400 to 25,000 g / mol.

4. A compound according to at least one of claims 1 to 3, characterized in that all radicals R ^{4 are} either cyclohexyl or isopropyl radicals or H.

5. A compound according to any one of claims 1 to 4, obtained by reacting a compound of formula (III)

RaXxY _y (IN) with R, X, Y, a, x, y and y 'as defined for formula (I) and with the proviso that x + y is greater than or equal to 3, with a compound of formula (IV)

R ⁴ -N = C = NR ⁴ (IV) with R ⁴ as defined for formula (I),

is reacted, wherein the molar ratio of the compounds of formulas (III) to compounds of formula (IV) is at least 1 to 2.

6. A process for the preparation of compounds according to claim 1, characterized in that a compound of formula (III)

R g _{X x} Y _y (III) with R, X, Y, Y, a, x, y and y 'as defined for formula (I) and with the proviso that x + y is greater than or equal to 3, with a compound of the formula (IV)

R ⁴ -N = C = NR ⁴ (IV) with R as defined for formula (I),

7. Use of compounds of the formula (Ia)

RcXxX YyYy (la) with

XR ¹ ₂ N-CH _:

NR ⁴ NR ⁴ ₂

-NR ⁴ -C -N = C

NR ' ² or NR ⁴ ,

R ¹ = identical or different alkyl radicals, - [CnH ₂ nO] _d -H or -C (O) R ² , preferably alkyl radicals having 1 to 3 carbon atoms or -H, particularly preferably -H, with n = 2, 3 or 4 , preferably n = 2 or 3, d = 1 to 20, preferably 1 to 10,

R ^1b = R ¹ or C (NR ⁴ ₂ ) (NR ⁴ ), preferably R ¹ ,

0 or 1, preferably 0

0 to 300, preferably 1 to 90, in particular> 2 to 30

0 to 150, preferably 0 to 50, in particular 2 to 25,

0 to 300, preferably 1 to 90, in particular 2 to 30, y '= 0 to 300, preferably 0.5 to 90, in particular 1 to 30,

R ^{4 is the} same or different alkyl or aryl radical or H,

Z = a + b a cohesive organic radical, preferably a cyclohexyl radical or a radical -

(CH ₂ ) _e - with e = 3, 4, 5 or 6,

a = 0 to 3,

b = 0 to 3 and

a + b is greater than or equal to 1,

as a formaldehyde scavenger in the preparation of a polyurethane system, in particular a polyurethane foam.

8. Use according to claim 7, characterized in that as the compound of formula (Ia) a compound according to any one of claims 1 to 5 in the preparation of a polyurethane system, in particular a polyurethane foam, is used.

9. Use according to claim 8 or 9, characterized in that the compounds according to formula (Ia) or (I) a reaction mixture which one or more organic isocyanates having two or more isocyanate functions, one or more polyols having two or more opposite Isocyanate-reactive groups, catalysts for the reactions isocyanate-polyol and / or isocyanate-water and / or the isocyanate trimerization, water, optionally physical blowing agents, optionally flame retardants and optionally further additives, is added.

10. A polyurethane system prepared according to the use according to any one of claims 7 to 9.

11. A polyurethane system according to claim 10, characterized in that it comprises from 0.05 to 10% by mass, based on the total composition of the polyurethane system, of compounds of the formula (I) or (Ia).

12. A polyurethane system according to any one of claims 10 or 11, characterized in that the polyurethane system is a rigid polyurethane foam, a flexible polyurethane foam, a viscoelastic foam, an HR foam, a semi-rigid polyurethane foam, a thermoformable polyurethane foam or an integral foam, preferably a polyurethane HR foam ,

13. Use of polyurethane systems according to at least one of claims 10 to 12 as refrigerator insulation, insulation board, sandwich element, pipe insulation, spray foam, 1- & 1, 5-component foam foam, imitation wood, model foam, packaging foam, mattress, furniture upholstery, automotive seat cushion, headrest , Dashboard, automotive interior trim, automotive headliner,

Sound absorption material, steering wheel, shoe sole, carpet back foam, filter foam, sealing foam, sealants and adhesives or for the production of corresponding products.