EP2376555A1

EP2376555A1 - Method for producing cold foams

Info

Publication number: EP2376555A1
Application number: EP09795966A
Authority: EP
Inventors: Martin Glos; Frauke Henning; Mladen Vidakovic
Original assignee: Evonik Goldschmidt GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2009-01-14
Filing date: 2009-12-14
Publication date: 2011-10-19
Also published as: WO2010081601A1; US20110306694A1; DE102009000194A1

Abstract

The invention relates to compositions comprising linear siloxanes, comprising only one further organically modified group in addition to the Si-alkyl substitution in the siloxane chain, wherein said group is bonded to a terminal silicon atom, and to the use thereof for producing polyurethane cold foams.

Description

Process for the production of cold foams

The invention relates to the production of polyurethane cold foams using linear polyethersiloxanes.

Polyurethane cold foams are also referred to as "cold foams" or "high-resilience-foams (HR-foams)".

Highly elastic polyurethane cold foams find versatile use for the production of mattresses, upholstered furniture or car seats. They are prepared by reacting isocyanates with polyols. Special siloxanes or siloxane surfactants serve to stabilize the expanding foam in the production of polyurethane cold foams. They ensure that a regular cell structure is formed and no disturbances in the foam occur.

State of the art:

Various structures are used as siloxanes.

US 2007/0072951 describes siloxanes which carry two terminal silanol units and their use in the production of polyurethane cold foam.

EP 1 753 799 A1 describes the preparation of

Polyurethane foam using siloxanes, which carry two terminal OH functions, wherein the OH function is bonded via an alkylene unit to the silicon atom.

When using siloxane structures bearing OH functions or other isocyanate-reactive groups, the siloxane becomes into the polymer matrix during foaming is therefore no longer available as surfactant or surfactant. Especially if the siloxane carries several reactive groups, it can additionally have a crosslinking effect. As a result, there is an increased risk that the cell opening is not strong enough and the foam shrinks on cooling after the foaming.

EP 1 095 968 A1 describes the preparation of cold foams using polydimethylsiloxanes which have a particularly narrow chain length distribution and therefore consist of more than 90% of siloxanes having the chain lengths N = 7-9. These siloxanes do not react in the polymer matrix, and therefore their surfactant properties are retained until the end of foaming. However, with the use of polydimethylsiloxanes, the problem may arise that these substances later emit from the foam, which is undesirable especially in automotive applications.

DE 3234462 C1 describes a process for the preparation of highly elastic cold-curing polyurethane foams, wherein

Polyether-modified siloxanes are used which are 4-25

Containing silicon atoms are modified with 1.5 to 10 polyether units in the S i 1 o x a n molecule and the

Polyether units of different proportions and oxyethylene (EO) and oxypropylene (PO) units included. No polyether modified siloxanes containing less than 1.5 modifications per molecule are described herein.

Thus, siloxanes with very different structural features are used, since the tasks of the siloxane in foaming can also be very different.

On the one hand, in the foaming, the return of the

Foam are reduced. On the other hand, after reaching the maximum foam height, sufficient cell opening should take place. In addition, the mixture to be foamed often has to be complicated, especially in the case of foam molding Cover flow paths and should have no defects in the foam structure after completion of foaming. Another requirement is the reduction of volatiles that escape from the finished foam. Therefore, there is a desire for siloxanes that contribute as little as possible to these emissions.

There is therefore a need for compositions containing siloxane structures that can meet these complex and diverse requirements.

Surprisingly, it has been found that the object according to the invention can be achieved by using linear siloxanes which, in addition to the Si-alkyl substitution in the chain, contains only one further organomodifying group, this group being bonded to a terminal silicon atom.

The compositions according to the invention contain siloxanes which can be described by the general formula (I)

in which

R ^{1 are} identical or different, straight or branched, aliphatic or aromatic, optionally halogenated, optionally unsaturated hydrocarbon radicals having 1 to 8 carbon atoms, preferably with a carbon atom ^¬ or a methyl group, are,

k is 0 to 30, preferably 0 to 10, wherein k in the presence of only one compound of formula (I), the actual number of labeled with the index k units and in the presence of multiple compounds of formula (I) represents the mean of the number of units

represents a group of the formula A-B-D-Q, wherein

A is an oxygen atom, a CH ₂ group or a CH = CH group,

B is a CH ₂ group or a divalent radical selected from linear or branched, saturated, mono- or polyunsaturated alkyl, aryl, alkylaryl or arylalkyl-oxy groups having 2 to 20 carbon atoms or a group of the formula -CH _{2 is} -O- (CH ₂ ) 4 -O- (which inserts as A-CH ₂ -O- (CH ₂ ) ₄ -ODQ into R ² ,

D is a group of the general formula (II)

- (C ₂ H ₄ O) _n (C ₃ H ₆ O) o (C ₁₂ H ₂₄ O) p (C ₈ H ₈ O) _q (C ₄ H ₈ O) _r - (II)

is, with n, o, p, q and r independent integers from 0 to 50, wherein the sum of the indices n + o + p + q + r is greater than or equal to 3 and the general formula (II) is a statistical oligomer or a block oligomer (wherein in formula (II) Ci ₂ H ₂₄ O is dodecene oxide and C ₈ H ₈ O is styrene oxide) and

Q is a radical selected from hydrogen, linear or branched, saturated, mono- or polyunsaturated, alkyl, aryl, alkylaryl or arylalkyl groups having 1 to 20 carbon atoms, optionally containing one or more heteroatoms, optionally one or more

Containing carbonyl groups, optionally with one modified ionic organic group which may contain, for example, the heteroatoms sulfur, phosphorus and / or nitrogen,

or technical compounds containing these compounds or consisting of at least one compound of the formula (I) in the preparation of polyurethane cold foams

describe.

As is apparent from the definition of the radical R ^2, the connection of the group R ² through a carbon atom (SiC linkage) or an oxygen atom (Si-O-linkage) can be carried out.

The composition preferably comprises or consists of compounds of the formula (I) in which all radicals R ^{1 of} the general formula (I) are methyl groups. Preferably, the composition comprises compounds of the formula (I) or consists of these in which the radical R ^{1 of} the general formula (I) is methyl, p = q = r = 0, the sum of the indices n + o greater or is equal to 3 and Q is selected from the group comprising hydrogen and

-CH ₃ -C-CH ₃

- (CH ₂ ) ₃ -CH ₃ OR ⁴

- C-CH-CH-C-OH

-CH-CH = CH ₂ Il ² Il

O O

in which

M ^{w + is} a w-valent cation with w = 1, 2, 3 or 4, in particular K ⁺ , Na ⁺ , NH ₄ ⁺ , (1C ₃ H ₇ ) NH ₃ ⁺ or (CHa) ₄ N ⁺ and

R ^{4 is} hydrogen or an optionally branched aliphatic radical having 1 to 20 carbon atoms,

R ⁵ and R ^{6 represent the} same or different, bridged or unbridged, branched or unbranched aliphatic radicals,

G is an oxygen atom, NH or an NR ⁷ group, where R ^{7 is} a monovalent alkyl group,

L is a divalent branched or unbranched, optionally oxygen and / or nitrogen-containing, alkyl radical, preferably a 3 to 6

Carbon atoms and 0 to 1 nitrogen atoms. Preferably, the composition comprises compounds of the formula (I) or contains those in which the radical R ^{1 of} the general formula (I) stands exclusively for methyl groups, p = q = r = 0, the sum of the indices n + o greater or is equal to 3, and Q is selected from the group comprising hydrogen, acetyl, methyl, ethyl, butyl and allyl radicals.

It is known to the person skilled in the art that the compounds are present in the form of a mixture with a distribution governed essentially by statistical laws. For example, in the composition may be a mixture of compounds of formula (I) with k = 1, 2, 3 and 4, etc. For the purposes of the invention, it has been found to be particularly advantageous if the compounds of the general formula (I) are used as a mixture. It can then be dispensed with a complex separation.

In a preferred embodiment of the use according to the invention siloxanes of the formula (I) are used in which the radical A is a CH ₂ group. In this off ^¬ guide form the connection of the radical R ² via a SiC linkage takes place.

In a further preferred embodiment of the use according to the invention siloxanes of the formula (I) are used in which the radical A is an oxygen atom. In this embodiment, the attachment of the radical R ² takes place via an Si-OC linkage.

The preparation of these siloxanes is described in the German, non-prepublished patent application DE 10 2007 046736.4, which is fully incorporated by reference and thus part of the description of this application.

The use of these siloxanes in the production of polyester polyurethane foams is also described here. As a rule, siloxanes used in the production of polyester polyurethane foams are not suitable for the production of polyurethane old foams. Therefore, it was all the more surprising that the siloxanes according to the invention can fulfill the object set here.

The present invention therefore provides the use of a composition comprising a siloxane of the formula (I), as described in DE 10 2007 046736.4, for the production of polyurethane old foams.

The siloxanes used according to the invention or compositions and processes for their preparation are described below by way of example, without the invention being restricted to these exemplary embodiments. Given below, ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their contents are intended to form part of the disclosure content of the present invention.

In addition to the compounds of the formula (I), the composition used according to the invention may contain one or more difunctional compounds of the general formula (II)

(II) exhibit. These compounds may be caused by the synthesis of the by-product of the monofunctional polyether siloxanes according to the invention. By choosing suitable reaction parameters, the occurrence of this undesired by-product can be largely avoided.

In addition to the compounds of the formula (I), the composition used according to the invention may comprise one or more compounds of the general formula (III)

with R ¹ as defined in claim 1 and t = 0 to 20, preferably 1 to 10, wherein t in the presence of only one compound of formula (III), the actual number of labeled with the index t units and in the presence of several compounds of formula (III) represents the average of the number of units.

The proportion of siloxanes of the formula (III) to monofunctional compounds of the formula (I) is preferably <or =

25 mass%, preferably ≤ 15 mass%, most preferably ≤ 10 mass%. However, according to the invention it is also possible to use compositions which have no compounds of the formula (III).

Another object of the invention are compositions containing siloxanes of the formula (I), (II) and / or (III).

Preference is given to those compositions which are free of siloxanes of the formula (II).

Another object of the invention are compositions containing siloxanes of the formula (I) and (III). There are a variety of high elastic polyurethane flexible foam production processes which are described in detail in the literature. Thus, in the published patent application DE 25 33 074 A1, which is fully incorporated by reference, a number of references have already been specified which describe the large-scale production of flexible polyurethane foams.

Furthermore, the production of flexible polyurethane foams in Becker / Braun, Plastics Handbook, Volume 7 (Editor: G. Oertel), Polyurethane, Carl Hanser Verlag, Munich; Vienna, 2nd edition 1983, to which reference is made in its entirety.

In the production of flexible polyurethane foams, depending on the reactivity of the raw materials, a distinction is made between hot-melt polyurethane foams (in the following: hot foams) and foamed polyurethane foams (in the following: cold foams), the terms deriving from the foaming of the foams. Thus, it is necessary in the production of hot foams after the molding process due to the low reactivity of the raw materials to heat the foam in the mold at elevated temperature, for example of> 90 ⁰ C, for complete crosslinking; these foams are therefore called hot foams.

The development of highly reactive polyether polyols and optionally the additional use of crosslinkers, however, make it possible to carry out the production of the foam in the mold due to the rapid curing with less heat. Such foams are therefore called cold foams.

In addition to the foaming form, it is also possible to perform the foaming after the block process, for what the terms cold and hot foam have also become common.

Because of the different raw materials, cold foams have very typical physical properties that distinguish them from hot foams.

The cold foams have:

(a) a latex-like handle,

(b) an increased elasticity compared to the conventional hot foams, which is why these foams are also referred to as "high resilience foams" (HR foams),

(c) a different from the hot foam compression hardness characteristic (higher SAG factor) and thus contribute

Use as upholstery material a better seating comfort (furniture foam),

(d) good long-term performance with little tendency to fatigue, which is of particular interest in the automotive sector,

(e) better flame retardancy than conventional hot foams due to their melting behavior,

(f) more favorable energy balance and shorter tool life in foam molding.

Another important feature of the cold foams is the "ball re-bound" rebound resilience A method for determining rebound resilience is described, for example, in ISO 8307. A defined-mass steel ball is dropped from a certain height onto the specimen and then the height Typical values for a cold soft foam are in the range of more than 55%, while hot foams or polyurethane ester foams, also referred to below as ester foams, have only rebound values of a maximum of 30% -48%. For the preparation of a polyurethane soft foam is a

Mixture of polyol, polyfunctional isocyanate,

Amine activator, tin, zinc or other suitable metal-containing catalysts, stabilizer, propellant usually water for the formation of CO ₂ and optionally an addition of physical blowing agents, optionally with the addition of further additives, such as flame retardants,

Color pastes, fillers, crosslinkers or other conventional processing aids implemented.

The crucial difference to the hot foam is in the cold foam production in that on the one hand highly reactive polyols and optionally low molecular weight crosslinkers are used, wherein the function of the crosslinker can also be taken over by higher-functional isocyanates. Thus, even in the expansion phase (CO ₂ formation from -NCO and H ₂ O) of the foam, the reaction of the isocyanate groups with the hydroxyl groups occurs. This rapid polyurethane reaction leads to a relatively high intrinsic stability of the foam during the blowing process via the viscosity increase.

Consequently, polyurethane flexible foams are highly elastic foams in which edge zone stabilization plays a major role. Due to the high intrinsic stability, the cells are often not opened sufficiently at the end of the foaming process and it still has to be pressed on mechanically.

Here, the necessary Aufdrückkraft is a measure of the open cell. Desirable foams are high

Open cell, which only require low pressure forces. When mold foaming

Polyurethane cold-cure foams as opposed to

Polyurethane hot foams at a temperature, for example, of <90 ⁰ C prepared. The siloxanes used as additives are usually not used as pure substances, but incorporated as a component in a corresponding formulation in order to improve the meterability or incorporability into the reaction matrix. Thus, DE 2356443 describes various organic substances for the preparation of aralkyl-modified siloxane oils containing formulations. WO 2008/071497 A1 describes formulations of siloxanes which are water-based. EP 0839852 B1 describes formulations of siloxanes which contain vegetable oils.

The siloxane-containing cold foam stabilizer formulation according to the invention has advantageous properties for controlling cell size and cell size distribution as well as edge zone regulation.

In the block foaming of polyurethane flexible foams, in addition to the foam stabilization and regulation of the zeolite size distribution, the necessary cell opening at the right time and to the right extent is the actual problem. If the cell opening is too early or too late, the foam may collapse or shrink. If a foam is not sufficiently open-celled, mechanical pressing can cause problems.

Additional requirements arise in the production of a flexible polyurethane soft foam body because the expanding reaction mixture has to overcome relatively wide flow paths in order to fill the entire mold volume. Here, it can easily lead to the destruction of whole cell aggregates on the mold walls or introduced inserts, so that under the foam skin cavities arise. Another critical zone is located in the area of the vents. Excess propellant gas too high speed past the cell aggregates, this leads to partially collapsed zones.

Advantageously, the cold foam stabilizer formulation according to the invention has the following advantages: adequate stabilization of the foam,

Stabilization against the influences of shear forces, stabilization of the marginal zone and the skin, - control of the cell size and the cell size distribution as well as the avoidance of an increased closed cell-cell-size.

Polyurethane cold foams may e.g. be prepared by the reaction of a reaction mixture consisting of

a) a polyol which carries on average at least two hydroxyl groups per molecule,

b) a polyisocyanate carrying on average two or more isocyanate groups per molecule, the polyol and the polyisocyanate constituting most of the reaction mixture and the ratio of the two components being suitable for producing a foam,

c) a blowing agent in small amounts, which is sufficient for the foaming of the reaction mixture,

d) a catalytic amount of a catalyst for producing the polyurethane foam, this usually consists of one or more amines, and

e) a foam stabilizer consisting of siloxanes and / or other surfactants, which sufficiently stabilizes the foaming mixture. Thus, the siloxanes of the general formula (I) can also be used as stabilizer, alone or in combination with further Si-containing or non-Si-containing surfactants. The siloxanes of the general formula (I) can also be diluted in suitable solvents in order to simplify the meterability or to improve the incorporability into the reaction mixture.

Accordingly, the compositions used according to the invention

a) a polyol which preferably carries on average at least two hydroxyl groups per molecule,

b) a polyisocyanate which on average preferably carries two or more isocyanate groups per molecule, polyols and polyisocyanates constituting the major part of the composition (reaction mixture) and the ratio of the two components should be suitable for producing a foam,

c) a blowing agent which is sufficient for the foaming of the reaction mixture,

d) a catalytic amount of a catalyst for preparing the polyurethane foam, preferably a catalyst containing one or more amines, and optionally e) at least one foam stabilizer other than compounds of the formula (I) which sufficiently stabilizes the foaming mixture,

contain.

It is possible to use the polyols, isocyanates, blowing agents, flame retardants, catalysts known from the prior art,

Additives and manufacturing processes are used. For example, the components mentioned in document EP 0 048 984, which is hereby incorporated by reference, can be used.

Another object of the invention are compositions containing siloxanes of the formula (I), and optionally (II) and (III) and / or other additives or adjuvants, which are familiar to the expert, such as: polyether polyols, polyester polyols as in the PU -Schaumherstellung be used, high-boiling solvents such as aliphatics and Aromatenschnitte, phthalates, Esteröle, glycerides, (alkyl) phenol derivatives, nonionic surfactants such as alcohol alkoxylates ^¬ example, anionic, cationic or amphoteric surfactants; Further examples of impact substances that may be contained in the siloxane compositions are described in the published patent application DE 2 356 443.

Other additives which may be present in the composition used according to the invention include flame retardants, cell openers, dyes, UV stabilizers, substances for preventing microbial attack and further additives which are obvious to the person skilled in the art and are not listed here.

The siloxanes used in the invention can be prepared in a known manner according to the prior art.

The siloxanes according to the invention are preferably prepared by the process described in DE 10 2007 046736.4.

Another object of the invention is a process for the preparation of polyurethane old foams using

Compositions containing the described linear siloxanes.

Another object of the invention is a polyurethane cold foam prepared by such a method using the linear siloxanes. Furthermore, articles of the invention are articles of daily use containing a polyurethane cold foam produced in this way, for example a car seat containing a corresponding polyurethane cold foam.

Another object of the invention is a commodity consisting of a process according to the invention using the composition containing linear siloxanes, produced polyurethane foam.

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. Further objects of the invention will become apparent from the claims, the disclosure of which is fully incorporated in this description.

Exemplary embodiments:

General:

The siloxanes according to the invention were prepared by the process described in DE 10 2007 046736.

The viscosities were, unless otherwise indicated, measured according to DIN 53015 at 20 ⁰ C with a falling ball viscometer Höppler.

Syntheses:

Preparation of the siloxanes:

Example 1:

Preparation of Siloxane A

A linear siloxane was prepared as described in Example 10 in DE 10 2007 046736.

Example 2:

Preparation of Siloxane B

A linear siloxane was prepared as described in example 10 in DE 10 2007 046736.

Example 3: Preparation of Siloxane C

In a four-necked flask equipped with a KPG stirrer, an internal thermometer and a reflux condenser, 743.5 g of an α, ω-dihydrogenpolydimethylsiloxane with a water content of 2, 69 eq / kg, 724.2 g

Hexamethyldisiloxan and 0, 86 ml Trif luomethansulf on acid for six hours at 40 ⁰ C stirred. After addition of 29, 4 g Sodium bicarbonate was stirred for 30 minutes at room temperature and the solid was filtered off.

In a next step be equipped with an overhead stirrer, an internal thermometer, a dropping funnel and a distillation apparatus in a four-necked flask, 53.0 g Golpanol® BEO from BASF in 46.4 g of butyl acetate and heated with stirring to 80 ⁰ C. 20 ppm of platinum in the form of a platinum (O) catalyst modified according to EP 1520870 were added, and 220 g of the hydrogen siloxane produced in the first step were added dropwise over a period of 2 hours. After the end of the Zudosage is stirred for a further two hours at 80 ⁰ C. The gas volumetric determined reaction conversion is quantitative. After distillation at 130 ⁰ C at the oil pump vacuum less than 2 mbar to obtain an orange-yellow colored, transparent product having a viscosity of 44.5 mPa * s.

Example 4:

Preparation of Siloxane D

A linear siloxane was prepared as described in example 11 in DE 10 2007 046736.

Example 5: Preparation of Siloxane E

In a four-necked flask equipped with a KPG stirrer, an internal thermometer and a reflux condenser 215.0 g of a butanol-started polypropylene glycol having an average molecular weight of 1800 g / mol for one hour at 110 ⁰ C heated. It is then cooled to 90 ⁰ C and 500 ppm of tris (pentafluorophenyl) borane are added. 47.0 g of the hydrogen siloxane from Example 4 are added dropwise with stirring at 90 ⁰ C in 30 minutes. The gas volumetric determined reaction conversion is quantitative after 2 hours. A clear, almost colorless product of viscosity 187.4 mPa * s is obtained. Example 6:

Preparation of Siloxane F

A linear siloxane was prepared by hydrosilylation of an allyl alcohol-started, EO-containing polyether with methyl endcapping (average molecular weight of 400 g / mol) with a Siloxanäquilibrat as described in DE 10 2007 046736 under Example 11, wherein after completion of the reaction the removal of the volatiles was omitted in a vacuum.

Example 7:

Preparation of Siloxane G

A linear siloxane was prepared by hydrosilylation of an EO / PO-containing polyether started with allyl alcohol (average molar mass of 500 g / mol, ca. 60% EO, 40% PO) with a siloxane equilibrate as described in DE 10 2007 046736 under Example 11 described, was omitted after completion of the reaction to the removal of the volatiles in vacuo.

Example 8: Preparation of Siloxane H

In a four-necked flask equipped with a KPG stirrer, an internal thermometer and a reflux condenser, 125.5 g of a starting with allyl alcohol polyethylene glycol having an average molecular weight of 400 g / mol with stirring to 70 ⁰ C heated and 6 ppm of platinum in the form of a EP 1 520 870 modified platinum (0) catalyst added. 130.0 g of the hydrogen siloxane from Example 4 are added dropwise in 30 minutes. The gas volumetric determined reaction conversion is quantitative after 2 hours. You get one clear, slightly yellow colored product with a viscosity of 39.2 mPa * s.

Example 9: Preparation of Siloxane I

In a four-necked flask equipped with a KPG stirrer, an internal thermometer and a reflux condenser are 166.3 g of an allyl alcohol-started polyether having an average molecular weight of 830 g / mol, 20 parts by weight of ethylene oxide and 80 parts by weight of propylene oxide with 85.0 g of the hydrogen siloxane from Example 4 with stirring to 70 ⁰ C heated and added 6 ppm of platinum in the form of a according to EP 1 520 870 modi fi ed P 1 atin (0) catalyst. The gas volumetric determined reaction conversion is quantitative after 2 hours. A clear, slightly yellow-colored product of viscosity 51.4 mPa * s is obtained.

Example 10: Preparation of Siloxane J

In a four-necked flask equipped with a KPG stirrer, an internal thermometer and a reflux condenser, 152.0 g of an allyl alcohol-initiated, methyl ether end-capped polyether having an average molecular weight of 600 g / mol, 40 parts by weight of ethylene oxide and 60 parts by weight of propylene oxide with stirring 70 ⁰ C heated and added 6 ppm of platinum in the form of a modified according to EP 1520870 platinum (O) - catalyst. 95.0 g of the hydrogen siloxane from Example 4 are added dropwise in 20 minutes. The gas volumetrically determined reaction conversion is 98% after 6 hours. A clear, slightly yellow-colored product of viscosity 22.5 mPa * s is obtained. Comparative Example 1 Preparation of Siloxane K (Not According to the Invention) As a result of the modified formulation, in this case the changed ratio of the components relative to one another in comparison to DE 2007046736, siloxanes of the formula (II) which are not according to the invention are prepared here. In a four-necked flask equipped with a KPG stirrer, an internal thermometer and a reflux condenser, 269.4 g of an α, ω-Dihydrogenpolydimethylsiloxans with a water ^¬ content of 2.69 eq SiH / kg, 16.2 g of hexamethyldisiloxane and 0.16 ml of trifluoromethanesulfonic acid for six hours at 40 ⁰ C stirred. After addition of 5.7 g of sodium bicarbonate was stirred for 30 minutes at room temperature and the solid was filtered off.

In a next step, in a four-necked flask equipped with a KPG stirrer, an internal thermometer and a reflux condenser, 183.7 g of an allyl alcohol-started polyether having an average molecular weight of 830 g / mol, 20 parts by weight of ethylene oxide and 80 parts by weight of propylene oxide having 65, 0 g of the hydrogen siloxane prepared in the first step was heated with stirring to 70 ⁰ C and added 6 ppm of platinum in the form of a modified according to EP 1520870 platinum (0) catalyst s added. The gas volumetric determined reaction conversion is quantitative after 2 hours. A clear, slightly yellow-colored product of viscosity 112 mPa * s is obtained.

Production of polyurethane chimney foam:

Formulation A:

100 parts of polyol having an OH number of 35 mg KOH / g and a molecular weight of 5000 g / mol, different parts of siloxane composition, the composition consisting of a 10% solution of the corresponding siloxane in a butanol-initiated polyppropylene glycol of molecular weight 700, 3 parts water, 2 parts triethanolamine, 0.6 parts TEGOAMIN® 33 and 0.2 part of diethanolamine and a mixture of 18.5 parts of polymeric MDI (Bayer's 44V20) and 27.7 parts of TDI (T80 = 80:20 toluene diisocyanate isomers of 2,4- and 2,6-diisocyanate).

Formulation B:

90 parts of polyol having an OH number of 32 mg KOH / g and a molecular weight of 5500 g / mol, 10 parts of a polymer polyol (43% styryol acrylonitrile polymer, SAN) having an OH number of 20 mg KOH / g and a molecular weight of 5000 g / mol, (different) parts siloxane composition consisting of a 10% solution of the corresponding siloxane in a butanol-initiated polyppropylene glycol molecular weight 700, 4 parts of water, 0.9 parts of diethanolamine, 0.4 parts of TEGOAMIN® MS 40, 0.06 part TEGOAMIN® BDE, 0.6 part glycerol and 46 parts isocyanate (T80 = 2,4- and 2,6-tolylene diisocyanate isomer mixture in the ratio 80:20).

Formulation C:

100 parts of polyol having an OH number of 29 mg KOH / g and a molecular weight of about 6000 g / mol, different parts Siloxanzusammensetzung consisting of a 10% solution of the corresponding siloxane in a butanol-initiated polyppropylene glycol of molecular weight 400, 4th , 1 part water, 1, 3

Parts Diethanolamine, 0, 08 parts TEGOAMIN® 33, 0, 05 parts TEGOAMIN® BDE, 0.2 parts Ortegol® 204, 0, 075 parts Kosmos® 29 and 1, 0 parts Voranol CP 1421 (from Dow) and 49 parts isocyanate (T80 = 2, 4- and 2, 6-Toluylendiisocyanat- isomer mixture in the ratio 80:20). Production of molded foam with formulation A:

The foams were prepared in the known manner by mixing all components except the isocyanate in a beaker, then adding the isocyanate and stirring rapidly at high stirrer speed. Was then added, the reaction mixture in a cuboid shape with dimensions of 40x40x10 cm, which was heated to a temperature of 40 ⁰ C and allowed to cure the composition when formulated for 10 minutes. Subsequently, the pressing forces were measured. Here, the foams were compressed 10 times to 50% of their height. Here is the 1. Measured value (AD 1 in Newton) is a measure of the open-cell nature of the foam. Subsequently, (manual) was completely pressed in order to be able to determine the hardness of the pressed-on foam at the 11th measured value (AD 11 in Newton). Thereafter, the foams were cut open to assess skin and marginal zone and to determine cell number (ZZ).

The following table summarizes Examples 11-13. These are the ratings, dosage of the siloxane composition in parts per hundred parts of polyol (pphp) and the particular siloxane used.

Table molded foam formulation A:

Production of molded foam with formulation B:

The foams were prepared in the known manner by mixing all components except the isocyanate in a beaker, then adding the isocyanate and stirring rapidly at high stirrer speed. Then, the reaction mixture was put in an industrially used mold for a car seat, which was heated to a temperature of 65 ° C, and allowed to cure the mass for 6 minutes. Subsequently, the compressibility (AD) of the foam was evaluated to be 1-10, with the value 1 representing very open 11 i and the value 10 a very closed cell foam. In addition, the flow (FL) of the foaming mass was rated with values of 1 to 5, where 1 stands for very good and 5 for very poor flow. Especially at bottlenecks in the form these effects come to light. The foams were then cut open to assess the quality (skin and marginal zone) and to determine the number of cells (ZZ). The following table summarizes Examples 14 to 23 and Comparative Examples 2 and 3. These are the ratings of the particular siloxane used and the dosage of the siloxane composition in pphp.

Table molded foam formulation B:

This shows that good foaming qualities are achieved with the siloxanes according to the invention in a broad concentration range, while with siloxanes of the formula (II) which are not according to the invention the quality is markedly worse since the foams become too closed and tend to shrink.

Production of block foam with formulation C:

The foams were prepared in the known manner by mixing all components except the isocyanate in a beaker, then adding the isocyanate and stirring rapidly at high stirrer speed. Then the reaction mixture was placed in a paper-lined container with a footprint of 28x28 cm. The height of rise (SH in cm) and relapse (RF in cm) were determined. The blowing off (AB) of the foam was rated at 0-3, with 0 for bad and unrecognizable and 3 was awarded for very strong blow off, with values of 1-2 are desired.

Relapse is the decrease of the height of rise in cm 1 minute after reaching the maximum rise height.

Blowing off is the release of the propellant gases from the opened cells of the foam.

After curing of the foam, it was cut open and the number of cells (currently in cm-1) was determined, and the quality of the foam (cell size distribution, edge zones) was generally assessed.

The following table summarizes examples 24 to 27. These are the ratings, the particular siloxane used and the dosage of the siloxane composition in pphp.

Table block foam formulation C:

These examples show that the siloxanes according to the invention are also suitable for producing good quality HR Bloch foams.

Claims

Claims:

1. Use of compositions containing linear siloxanes, which in addition to the Si-alkyl substitution in the chain contain only one further organomodifying group which is bonded to a terminal silicon atom, for the production of polyurethane old foams.

2. Composition containing linear siloxanes of the formula (I)

where R ^{1 are} identical or different, straight-chain or branched, aliphatic or aromatic, optionally halogenated, optionally unsaturated hydrocarbon radicals having 1 to 8 carbon atoms, preferably having one carbon atom, k is 0 to 30, preferably 0 to 10, where k is

Presence of only one compound of the formula (I) represents the actual number of units marked with the index k and in the presence of several compounds of the formula (I) represents the average of the number of units, R ^{2 represents} a group of the formula ABDQ, where

A is an oxygen atom, a CH ₂ group or a

CH = CH group,

B is a CH ₂ group or a bivalent radical selected from linear or branched, saturated, mono- or polyunsaturated Alkyl, aryl, alkylaryl or arylalkyl

Oxy groups having 2 to 20 carbon atoms or a group of the formula -CH ₂ -O- (CH ₂ ) ₄ -O- is

(which inserts as A-CH ₂ -O- (CH ₂ ) ₄ -ODQ in R ² ,

D is a group of the general formula (II)

Q is a radical selected from hydrogen, linear or branched, saturated, mono- or polyunsaturated, alkyl, aryl, alkylaryl or arylalkyl groups having 1 to 20 carbon atoms, optionally containing one or more heteroatoms, optionally containing one or more carbonyl groups, optionally modified with an ionic organic group which may contain, for example, the heteroatoms sulfur, phosphorus and / or nitrogen,

or these compounds containing technical mixtures or consisting of at least one compound of formula (I).

3. Composition comprising linear siloxanes according to claim 2 with a radical R ² of a via a carbon atom

(SiC linkage) or an oxygen atom (SiOC linkage) is linked.

4. Compositions containing compounds according to claims 2 or 3, characterized in that all radicals R ^{1 of} the general formula (I) are methyl groups. Compositions containing compounds according to claims 2 or 3, characterized in that p = q = r = 0, the sum of the indices n + o is greater than or equal to 3 and Q is selected from the group comprising hydrogen and

-CH ₃ -C-CH ₃

- (CH ₂ ) ₃ -CH ₃

-

-CH-CH = CH ₂ ° C-CH-C fH-C-OH II ² II

O O

- SO, H

- C-CH = CH-C-OH

-SO ₃ ^" V _W M ^{W +} Il II OO

in which

M ^{w + is} a w-valent cation with w = 1, 2, 3 or 4, in particular K ⁺ , Na ⁺ , NH ₄ ⁺ , (1C ₃ H ₇ ) NH ₃ ⁺ or (CH _a ) ₄ N ⁺ , and

G is an oxygen atom, NH or an NR ⁷ group, wherein R ^{7 is} a monovalent alkyl group, and L is a divalent branched or unbranched, optionally oxygen and / or nitrogen-containing, alkyl radical, preferably a 3 to 6

Carbon atoms and 0 to 1 nitrogen atoms.

6. The composition according to at least one of claims 4 and

5, characterized in that it contains compounds of formula (I) in which the radical R ^{1 of} the general formula (I) stands exclusively for methyl groups, p = q

= r = 0, the sum of indices n + o is greater than or equal to 3, and Q is selected from the group comprising hydrogen, acetyl, methyl, ethyl, butyl and allyl radicals.

7. The composition according to at least one of claims 3 to

6, characterized in that in the formula (I) the radical A is a CH ₂ group and thus the connection of the radical R ² via a SiC linkage takes place.

8. The composition according to at least one of claims 3 to 6, characterized in that in the formula (I), the radical A is an oxygen atom and thus the attachment of the radical R ² via a Si-OC linkage.

9. Use of compositions containing linear siloxanes according to at least one of claims 2 to 8 in the production of polyurethane old foams.

10. Compositions comprising the linear siloxanes of the formula (I), (II), and / or (III)

(II)

wherein R ^{1 is} as defined in claim 2 and t = 0 to 20.

11. The composition according to claim 10, characterized in that the content of linear siloxanes of the formula (III) <or = 25% by mass.

12. The composition according to claim 10 or 11, characterized in that no siloxanes of the formula (II) are contained.

13. Compositions according to at least one of claims 4 to 12 comprising linear siloxanes of the formula (I), and optionally (II) and (III) and / or further additives or auxiliaries selected from the group of polyether polyols, polyester polyols, high-boiling solvents, phthalates, Ester oils, glycerides,

(Alkyl) phenol derivatives, nonionic surfactants and / or alcohol alkoxylates.

14. Compositions according to at least one of claims 4 to 13, characterized in that flame retardants,

Cell openers, dyes, UV stabilizers, substances to prevent microbial attack are included.

15. A process for the preparation of polyurethane old foams using linear siloxanes according to at least one of claims 2 to 14.

16. Polyurethane cold foam prepared by a process according to claim 15 using linear siloxanes according to at least one of claims 2 to 14.

17. Utility item containing a

Polyurethane cold foam according to claim 16.

18. A car seat containing a polyurethane cold foam according to claim 16.

19. Utility article consisting of a polyurethane cold foam according to claim 17.