DE10245576A1 - A catalyst agent obtainable by reaction of a catalytically active compound with polyisocyanates useful in the preparation of polyurethanes by thermal desorption with an emission value of less than 20 ppm - Google Patents

Abstract

A catalyst agent obtainable by reaction of (i) a catalytically active compound which accelerates the urethane reaction and has NH-, NH2- and/or OH groups with (ii) polyisocyanates, where (i) and (ii) are so selected that reaction of components (i) and (ii) results in compounds with urethane- and/or urea groups which are not bonded to aromatic hydrocarbon groups and the molecular weight of the catalyst agent is higher than 750 g/mole is new. Independent claims are include for: (1) a polyurethane obtainable by reaction of:(a) polyisocyanates with (b) compounds with H atoms reactive to isocyanates, and (c) a catalyst agent as above; (2) An automobile dashboard, side coverings (sic) and/or arm rests containing polyurethane.

Description

The invention relates to a catalyst agent, available by reacting (i) a catalytically active compound which the urethane reaction accelerates and NH, NH2 and / or OH groups has, with (ii) polyisocyanates, wherein catalytically active compound (i) and polyisocyanate (ii) are chosen so that the reaction leads to compounds with urethane and / or urea groups, the are not bound to aromatic hydrocarbon groups. The The molecular weight of the catalyst agent is greater than 750 g / mol. The invention further relates to the use of the catalyst agent for the production of polyurethanes with improved emissions and Aging behavior.

In the manufacture of polyurethanes (PUR), built-in catalysts are increasingly being used to reduce emissions, especially amine emissions. Most of the built-in catalysts known in the prior art have primary and / or secondary hydroxyl and / or amino groups, which are generally formed by a short spacer based on an alkyl chain (CH ₂ groups and / or CHCH ₃ -CH ₂ groups) or an alkyl ether chain are separated from the catalytic center.

Modified, built-in are also Catalysts known. WO 94/2525 describes modified amine catalysts, by reacting a reactive tertiary amine and polyols with Isocyanate compounds can be obtained. The aim of the modification is an increase of catalytic activity.

WO 02/40568 also describes modified amine catalysts used to improve solubility properties by reacting a reactive tertiary amine and polyols with Isocyanate compounds are obtained, a polyisocyanate being used as the isocyanate the diphenylmethane series with a functionality of 2.5 to 4.0 becomes.

WO 02/48229 describes catalysts for the production of polyurethane foams by implementing a Catalyst system from a tertiary amine carbamate. It deals are low molecular weight catalyst systems, making it an unwanted Raising the fogging value of the resulting foam can come.

It turns out that many of the im Known prior art, built-in catalysts in the polyurethane be installed under the conditions of the emission tests at higher temperatures (from approx. 100 ° C) However, some of them are removed again and thus lead to emissions contribute. Furthermore, the known, built-in catalysts the effect that they are very different from volatile catalysts have a negative impact on the aging properties of PUR materials can. By dismantling the catalysts at higher temperatures, this becomes negative behavior obviously favored.

Object of the present invention it was therefore to modify built-in PUR catalysts in such a way that on the one hand they do not lead to emissions from PUR materials among the Conditions of emission tests contribute and secondly an improved Cause aging behavior of the PUR material.

This task could be solved by known, built-in PUR catalysts, the emissions and have poor aging behavior before the PUR reaction were coupled to isocyanate compounds, the used Isocyanate compounds have no free isocyanate groups that are covalently bound to aromatic groups.

• i) einer katalytisch aktiven Verbindung, welche die Urethanreaktion beschleunigt und sekundäre oder primäre Amingruppen und/oder Hydroxygruppen, d.h. NH-, NH2- und/oder OH-Gruppen aufweist, mit
• ii) Polyisocyanaten, wobei katalytisch aktive Verbindung (i) und Polyisocyanat (ii) so gewählt werden, dass die Umsetzung der Komponenten (i) und (ii) zu Verbindungen mit Urethan- und/oder Harnstoffgruppen führt, die nicht an aromatische Kohlenwasserstoffgruppen gebunden sind. Dabei weist das hergestellte Katalysatormittel ein Molekulargewicht von mehr als 750 g/mol auf.

The invention therefore relates to a catalyst agent obtainable by reaction

• i) a catalytically active compound which accelerates the urethane reaction and has secondary or primary amine groups and / or hydroxyl groups, ie NH, NH2 and / or OH groups
• ii) polyisocyanates, the catalytically active compound (i) and polyisocyanate (ii) being selected such that the reaction of components (i) and (ii) leads to compounds having urethane and / or urea groups which are not bound to aromatic hydrocarbon groups , The catalyst agent produced has a molecular weight of more than 750 g / mol.

The invention also relates to the use of the catalyst agent according to the invention for the production of polyurethanes with low emissions at elevated temperatures are.

• a) Polyisocyanaten mit
• b) Verbindungen mit gegenüber Isocyanaten reaktiven Wasserstoffatomen in Gegenwart von
• c) dem erfindungsgemäßen Katalysatormittel.

The invention also relates to polyurethanes and polyurethane molded parts such as dashboards, obtainable by reacting

• a) with polyisocyanates
• b) Compounds with hydrogen atoms reactive towards isocyanates in the presence of
• c) the catalyst agent according to the invention.

Finally, the subject of the invention the use of the polyurethanes according to the invention for the production of interior transport equipment.

So-called built-in polyurethane catalysts are generally suitable as catalytic compound (i), ie all compounds which on the one hand accelerate the reaction of isocyanates with compounds having hydrogen atoms reactive towards isocyanates and on the other hand NH-, NH ₂ - and / or Have OH groups, via which a covalent bond to the polyurethane matrix can take place.

Tertiary amines which have NH, NH ₂ and / or OH groups are preferably used as catalytically active compound (i). In general, the NH, NH ₂ and / or OH groups within the catalytically active compound should have a spatial distance from the catalytic center. The NH, NH ₂ and / or OH groups are preferably separated from the tertiary amine group by an alkyl chain or alkyl ether chain having at least two carbon atoms.

Examples of preferred catalytic Compounds (i) are N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether, 2- (2-dimethylaminoethoxy) ethanol, N, N-dimethylethanolamine, N, N-bis- (3-dimethylaminopropyl-) N-isopropanolamine, N- (3-dimethylaminopropyl-) N, N-diisopropanolamine, N, N-bis- (3-dimethylaminopropyl-) amine, N- (3-aminopropyl) imidazole, (3-dimethylaminopropyl) amine, N- (2-dimethylaminoethyl-) N-methylethanolamine, N- (2-hydroxypropyl) imidazole, dimethylaminohexanol.

As polyisocyanates (ii) general polyisocyanates with a functionality of at least two, preferably from more than two to five used.

It is an essential feature of the present invention that polyisocyanates (ii) are used the free isocyanate groups are not attached to aromatic hydrocarbon groups linked are.

The isocyanates can be in the pure compound or modified Form, for example in the form of uretdiones, isocyanurates, allophanates or biurets or in the form of urethane and isocyanate groups Implementation products, so-called isocyanate prepolymers, used become.

Examples include tetramethylene diisocyanate dimers and trimers, hexamethylene diisocyanate dimers and trimers and higher homologues, isophorone diisocyanate dimers and trimers, lysinalkyl ester diisocyanate, where alkyl is C ₁ to C ₁₀ , 2,2,4 or 2,4, 4-trimethyl-1,6-hexamethylene diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, 2-isocyanatopropylcyclohexyl isocyanate, 4-methyl-cyclohexane-l, 3-diisocyanate (H-TDI) or 4- Isocyanatomethyl-l, 8-octamethylenedü socyanat or mixtures thereof.

Dimers, trimers are preferred and / or higher Homologs of hexamethylene diisocyanate and other reaction products, such as allophanates or biurets of hexamethylene diisocyanate used. Biuretized or isocyanurated ones are particularly preferred Derivatives of hexamethylene diisocyanate with a functionality of more than 2.5 to 6, in particular 3.5 to 4, used.

An example of polyisocyanates that are not The isomers diphenylmethane diisocyanate are within the scope of the invention as well as the higher ones Homologues of it.

In a preferred embodiment the reaction of components (i) and (ii) in the presence of Polyols (iii) performed. Generally, the polyol component (iii) is used as a solvent for the catalyst component (i) used. The polyol component (iii) can, however, only after the reaction of component (i) and (ii) are added and then, if appropriate, not yet reacted reacted isocyanate groups of component (ii). The Composition of the polyol component (iii) is below Component b) described.

To a complete reduction in emissions and the best durability to achieve against aging conditions is the implementation of the Components (i) and (ii) generally ensure that all built-in groups of the catalysts on isocyanate groups of the component (ii) be connected. It is therefore preferred that in the reaction mixture of components (i) and (ii) and optionally (iii) the number the free OH and / or NH groups contained in components i) same size or is less than the number contained in component ii) NCO groups.

In a preferred embodiment components (i) and (ii) and optionally (iii) are chosen such that the resulting catalyst agent has a molecular weight of more than 750 grams per mole (g / mol), preferably from 800 to 5000 g / mol, particularly preferably from 900 to 2000 g / mol.

Especially when manufacturing Polyols (iii) are used in the form of a molecular weight distribution are present, the catalyst agent according to the invention can also be in the form a molecular weight distribution. In this case, refer the above information on the molecular weight refers to the number average Molecular weight. Even in the case of a molecular weight distribution has the catalyst agent of the invention essentially no ingredients that have a molecular weight less than 750 g / mol, preferably less than 800 g / mol, particularly preferably have less than 900 g / mol. If necessary, in small amounts of compounds less than that given above Molecular weight may be included, such impurities are generally in an amount of less than 2% by weight, preferred less than 1% by weight, particularly preferably less than 0.5% by weight, based on the total weight of the resulting catalyst agent, in front.

The catalyst agent according to the invention can be particularly effective can be used advantageously for the production of polyurethanes, those with increased Temperature are low in emissions. At elevated temperature there is one Understanding residence time of 1 hour at about 120 ° C.

In particular, the catalyst agent according to the invention is used for the production of polyurethanes which, according to the thermal desorption method according to DaimlerChrysler (PB VWL 709), have an emission value of the catalyst agent of less than 20 ppm, preferably less than 10 ppm, more preferably less have less than 5 ppm and in particular less than 1 ppm.

Furthermore, the catalyst agent according to the invention used for the production of polyurethanes, their mechanical Properties by thermal and / or wet-heat aging not so badly damaged are like using the unmodified, built-in catalysts.

In a preferred embodiment becomes the catalyst agent according to the invention used for the production of polyurethanes after wet / heat storage (72 hours at 90 ° C and 90% humidity) a compression set (DVR) according to DIN EN ISO 1856, from a maximum of 10%, preferably from 0 to 8%, particularly preferably have from 0 to 7%.

• a) Polyisocyanaten mit
• b) Verbindungen mit gegenüber Isocyanaten reaktiven Wasserstoffatomen in Gegenwart von
• c) einem erfindungsgemäßen Katalysatormittel.

At elevated temperatures, low-emission polyurethanes can be obtained by implementing

• a) with polyisocyanates
• b) Compounds with hydrogen atoms reactive towards isocyanates in the presence of
• c) a catalyst agent according to the invention.

Furthermore, the implementation can still d) Blowing agents and e) additives are added.

In the polyurethanes according to the invention it can be compact or cellular polyurethanes, preferred are polyurethane foams. It can also be soft, semi-hard or act as hard polyurethane foams. The polyurethanes according to the invention preferably demonstrate the above-mentioned compression set Moist / heat storage on.

As isocyanates (a) can generally known (cyclo) aliphatic and / or in particular aromatic polyisocyanates be used. For the production of the composite elements according to the invention Aromatic diisocyanates are particularly suitable, preferably diphenylmethane diisocyanate (MDI) and tolylene diisocyanate (TDI). The isocyanates can Form of the pure compound or in a modified form, for example in Form of uretdiones, isocyanurates, allophanates or biurets, preferably in the form of urethane and isocyanate groups Reaction products, so-called isocyanate prepolymers, are used.

Suitable compounds with hydrogen atoms (b) which are reactive toward isocyanates are compounds which contain two or more reactive groups selected from OH groups, SH groups, NH groups, NH ₂ groups and CH-acidic groups, such as (3 Depending on the choice of component (b) in the context of this invention, the term generally includes polyisocyanate polyadducts, for example also polyureas.

Expediently as a component (b) Compounds with a functionality of 1.8 to 8, preferably 2 to 6, and a molecular weight of 300 to 8000, preferably used from 400 to 4000. proven have e.g. Polyether polyamines and / or preferably polyols, selected from the group of polyether polyols, polyester polyols, polythioether polyols, Polyesteramides, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic polycarbonates or mixtures of at least two of the mentioned polyols.

Polyester polyols are preferably used and / or polyether polyols. Polyether polyols are particularly preferred used, especially those that have at least 10% primary hydroxyl groups exhibit. The hydroxyl number of the polyhydroxyl compounds is usually 50 to 1000. Furthermore, the compounds (b) in Mix with usual Chain extenders and / or Crosslinking agents are used.

As polyetherols (b), so-called low unsaturated Polyetherols can be used. Taking low unsaturation In the context of this invention, polyols are especially polyether alcohols containing unsaturated Compounds of less than 0.02 meq / g, preferably less than 0.01 meq / g, understood. Such polyether alcohols are mostly by Addition of alkylene oxides, especially ethylene oxide, propylene oxide and mixtures thereof, of at least difunctional alcohols in Presence of so-called double metal cyanide catalysts.

As component c) above described catalyst agent according to the invention used. Generally, the catalyst agent is used in an amount from 0.1 to 40% by weight, preferably from 0.5 to 10% by weight, particularly preferably from 1 to 8% by weight, based on the total weight of the Components b) and c) and optionally d) and e) used.

Component c) can be used for the polyurethane reaction either component a) (isocyanate component) or the component b) (polyol component) or both are added.

As blowing agent (d) can Production of foamed Products generally known chemically or physically active Connections are used. As a chemical blowing agent water can preferably be used. Examples of physical Blowing agents are inert (cyclo) aliphatic hydrocarbons 4 to 8 carbon atoms under the conditions of polyurethane formation evaporate. The amount of blowing agent used depends on according to the desired density of the foams.

If appropriate, the reaction is carried out in the presence of auxiliaries and / or additives, such as cell regulators, separating agents, pigments, surface-active compounds and / or stabilizers against oxidati ven, thermal, hydrolytic or microbial degradation or aging.

For the production of the polyurethanes according to the invention components (a), (b) and (c) and optionally (d) and (e) implemented in such amounts that the equivalence ratio of NCO groups to the sum of the reactive hydrogen atoms 1: 0.8 to 1: 1.25, preferably 1: 0.9 to 1: 1.15. A relationship 1: 1 corresponds to an NCO index of 100.

The polyurethanes can be used as moldings getting produced. To do this, they are generally made using the one-shot process with the help of low pressure or high pressure technology in closed, expediently temperature-controlled molds. The output components are common at a temperature of 15 to 90 ° C, preferably of Mixed 20 to 35 ° C and optionally under increased pressure introduced into the closed mold. The mixing can mechanically using a stirrer or a stirring screw or under high pressure in the so-called countercurrent injection process carried out become. The mold temperature is advantageously 20 to 90 ° C, preferably 30 to 60 ° C.

The degrees of compaction for production the molded body with a densified marginal zone and cellular core, for example at the production of steering wheels, are generally in the range from 1.1 to 8.5, preferably from 2 to 7.

The low-emission polyurethanes according to the invention are preferred in the manufacture of interior transportation equipment, for example in the interior of automobiles, airplanes or trains, Use. The polyurethanes according to the invention are also used in the production of flexible foams, for example block flexible foams or Molded flexible foams, for example for the manufacture of mattresses.

The invention thus includes interior transport facilities, containing the catalyst agent according to the invention. examples for Interior fittings are dashboards, side panels, headlining, Hat racks, car seats, steering wheels, armrests, Head and side impact elements and roof modules. Also includes the invention mattresses containing the catalyst agent according to the invention.

The corresponding components are preferably from the following PUR

Foams built up: dashboards, Side panels, armrests based on a semi-rigid polyurethane foam with a compressive strength of more than 15 to less than 80 kPa according to DIN 53 421st

Car seats and mattresses based a flexible polyurethane foam with a compressive strength of 15 kPa or less according to DIN 53 421st

Steering wheels, based on integral soft polyurethane foams.

Roof modules made of glass fiber reinforced hard foam.

The present invention is intended to be accomplished by the following examples are illustrated.

Starting materials: Lupranol ^® 2047: Cell opener polyetherol with OH number 42 Lupranol ^® 2090: Reactive polyetherol with OH number 28 Polyol PP 50: Ethoxylated pentaerythritol with OH number 630 LupranatM 20 W: Polymer MDI with an NCO content of 31.2 Lupranat ^® MM 103: Carbodiimide modified 4,4'-MDI with NCO content 29.5 Lupranat®ME / MES: 4,4'-MDI, MES is stabilized against yellowing Lupranat ^® MI: Mixture of 2,4'- and 4,4'-MDI with an NCO content of 33.2 Basonat ^® HB 100: Biuretized HDI with NCO content from 22 to 23 Basonat ^® HI 100: Isocyanurated HDI with an NCO content of 21.5 of 22.5 Tegostab ^® B 8631: stabilizer Jeffcat ^® ZF10: N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethylether Jeffcat ^® ZR50: N, N-bis (3-dimethylaminopropyl) N-isopropanolamine Lupragen ^® N 206: Bis (2-dimethylaminoethyl) ether 70% solution in dipropylene glycol Lupragen ^® N 107: Dimethylaminoethoxyethanol.

Examples

Comparative Example 1

A polyol component made from 92 parts by weight of Lupranol® 2090 (Elastogran GmbH), 8 parts by weight of Polyol PP50 (Perstorp AB), 2.81 parts by weight of water, 0.26 parts by weight was used to produce a semi-rigid polyurethane foam. parts Jeffcat® ZF10 (Huntsman Corporation), 0.26 parts by weight potassium acetate (47% in ethylene glycol), 0.8 parts by weight of Jeffcat ZR50 ^® (Huntsman Corporation) with an isocyanate component consisting of a mixture of 31.5 Parts by weight of Lupranat ^® M 20 W (Polymer-MDI, Elastogran GmbH) and 68.5 parts by weight of a prepolymer (NCO content: 26%) made from Lupranat® MM 103, Lupranat ^® ME (Elastogran GmbH) and tripropylene glycol mixed at an index of 0.97 and the foaming mixture was placed in an aluminum mold with the dimensions 20 cm x 20 cm x 4 cm and heated to 44 ° C. and a pillow with a density of 100 kg / m3 was obtained.

For emission measurements using the thermal desorption method according to DaimlerChrysler (PB VWL 709) there were emissions in the fog value (1 h 120 ° C) from the Jeffcat ZR50 of 30 ppm.

Example according to the invention 2

Proceed as described in the comparative example. Instead of Jeffcat® ZR50 be 1.4 parts of an adduct of Jeffcat ZR50 ^® and Basonat® HB 100 (BASF Aktiengesellschaft) were used. In the preparation of the adduct, Jeffcat ZR50 and Basonat ^® HB 100 were combined in an equimolar amount, based on the NCO and OH groups present, with stirring at room temperature and then stirred at 80 ° C. for 1 h.

For emission measurements using the thermal desorption method according to DaimlerChrysler (PB VWL 709) there were no fog values Emissions from the Jeffcat® ZR50.

Comparative Example 3

Proceed as described in the comparative example. Instead of Jeffcat® ZR50, 1.2 parts of an adduct of Jeffcat ZR50 ^® and 2,4'-MDI used. In the preparation of the adduct, Jeffcat® ZR50 and 2,4'-MDI, dissolved in toluene, were combined in equimolar amounts, based on the NCO and OH groups present, with stirring at room temperature and then stirred at 80 ° C. for 1 h.

For emission measurements using the thermal desorption method according to DaimlerChrysler (PB VWL 709) there were emissions in the fog value from the Jeffcat® ZR50 of 230 ppm.

Comparative Example 3 thus showed that the connection of built-in catalysts to aromatic isocyanates was unsuccessful.

Comparative Example 4

For producing a molded flexible polyurethane foam were 641.5 g of a polyol component comprising 97 parts by weight Lupranol® 2090 3.0 parts by weight Lupranol ^® 2047 3.31 parts by weight water, 0.50 parts by weight Tegostab ^® B 8631 (Goldschmidt AG), 0.05 part by weight of Dabco ^® crystalline, 0.1 part by weight of Lupragen N 206 (BASF Aktiengesellschaft) and 0.84 part by weight of Lupragen ^® N 107 (BASF Aktiengesellschaft) 308.5 g MDI mixture, consisting of 47 parts by weight of Lupranat® MI (Elastogran GmbH), 42 parts by weight of Lupranat M 20 W and 11 parts by weight of Lupranat MES mixed with an index of 0.9 and that foaming mixture in a heated to 50 ° C mold with the dimensions 40 cm × 40 cm × 10 cm and the foam cushion removed after 5 min.

This foam had one without aging Rebound resilience of 67 % and a compression set (DVR), determined according to DIN EN ISO 1856, by 4.6%. After wet-heat aging (72 h, 90 ° C, 90% humidity) the rebound resilience was still 50 % and the DVR 14.8%.

Example according to the invention 5

Procedure as described in Comparative Example 4. Instead of Lupragen N 107, 2.43 parts by weight (based on the polyol component) of an adduct of Lupragen N 107 and Basonat® HI 100 (BASF Aktiengesellschaft) were used. In the preparation of the adduct, Lupragen N 107 and Basonat ^© HI100 were reacted in such a ratio that 67% of the NCO groups were reacted. Basonat ^© HI 100 was placed in the preparation at 30 ° C and Lupragen N107 was added dropwise with stirring at a temperature of 40 to 45 ° C within 105 min. The mixture was then stirred at 40 to 45 ° C for 60 min. The adduct was used in the foaming in the isocyanate component.

This foam has one without aging Rebound resilience of 69 % and a compression set (DVR) of 3.7%. After moist-heat aging (72 h, 90 ° C, 90% humidity) the resilience was still 58 % and the DVR 7.5%.

Claims (10)

Catalyst agent obtainable by reacting i) a catalytically active compound which accelerates the urethane reaction and has NH, NH ₂ and / or OH groups with ii) polyisocyanates, catalytically active compound (i) and polyisocyanate (ii) being chosen in this way be that the reaction of components (i) and (ii) leads to a compound with urethane and / or urea groups which are not bound to aromatic hydrocarbon groups and wherein the molecular weight of the catalyst agent is greater than 750 g / mol. Catalyst agent according to claim 1, characterized in that while or after the reaction of the catalytically active compound (i) with Polyisocyanates (ii) a iii) polyol is added. Catalyst agent according to claim 1 or 2, characterized in that the catalytically active compound (i) is tertiary amines which have NH, NH ₂ and / or OH groups. Catalyst agent according to one of claims 1 to 3, characterized in that within the built-in catalysts the NH, NH ₂ or OH groups are separated from the tertiary amino group by at least two carbon atoms. Catalyst agent according to one of claims 1 to 4, characterized in that in the implementation mixture the number the free OH and / or NH groups contained in components i) same size or less is like the number of NCO groups contained in component ii). Catalyst agent according to one of claims 1 to 5, characterized in that as polyisocyanates (ii) dimers, Trimers or higher Homologs of hexamethylene diisocyanate and allophanates or biurets of hexamethylene d socyanate or mixtures thereof can be used. Use of a catalyst agent according to a of claims 1 to 6 for the production of polyurethanes using the thermal desorption method according to DaimlerChrysler (PB VWL 709) an emission value of less than 20 ppm. Polyurethanes available by implementing a) with polyisocyanates b) connections with opposite Isocyanate reactive hydrogen atoms in the presence of c) a catalyst agent according to one of claims 1 to 6. Use of the polyurethanes according to claim 8 for the production of transportation interiors. Dashboard, side panel and / or armrest, containing polyurethanes according to claim 8th.