EP3768744A1

EP3768744A1 - Method for producing polyurethane soft foams

Info

Publication number: EP3768744A1
Application number: EP19711099.2A
Authority: EP
Inventors: Matthäus Gossner; Veronica-Alina FÄRBER; Lutz Brassat
Original assignee: Covestro Intellectual Property GmbH and Co KG
Current assignee: Covestro Intellectual Property GmbH and Co KG
Priority date: 2018-03-22
Filing date: 2019-03-19
Publication date: 2021-01-27
Also published as: WO2019180024A1; EP3543268A1; CN111902447A; US20210024681A1

Abstract

The invention relates to a method for producing polyurethane soft foams, in particular open-cell polyurethane soft foams based on polyether carbonate polyol and toluylene diisocyanate, wherein the resulting polyurethane soft foams have similar properties to the already known polyurethane soft foams and they are simpler and more sustainable in terms of their production.

Description

Process for the production of flexible polyurethane foams

The object of the present invention relates to a process for the production of flexible polyurethane foams, in particular open-cell foams

Flexible polyurethane foams based on Polyethercarbonatpolyol- and T oluylendiisocyanatbasis, wherein the resulting flexible polyurethane foams have similar properties as the previously known flexible polyurethane foams, but these are easier and more sustainable in their production.

To obtain flexible foams based on Polyethercarbonatpolyol- and Toluylendiisocyanatbasis with a desired Offenzelligkeit so far two different batches of Toluylendiisocyanatgemischen were used. The first batch is a mixture of 80% by weight 2,4-oluylene diisocyanate and 20% by weight 2,6-toluene diisocyanate obtainable by simple preparation, namely nitration and then reduction to amine and phosgenation. The second mixture consists of 67 wt .-% 2,4-tolylene diisocyanate and 33 wt .-% 2,6-T oluylendiisocyanat and in order to obtain the higher content of 2,6-T oluylendiisocyanat to be worked up cost and labor intensive. In this case, T oluylendiisocyanat crystallized from the mixture to increase the proportion of 2,6-T oluylendiisocyanat. The higher content of 2,6-toluene diisocyanate is necessary to increase the content of this compound in the reaction for the flexible polyurethane foams. The higher content of 2,6-tolylene diisocyanate is again necessary to obtain the desired open-celledness.

It was therefore an object of the present invention to find a system in which the use of the charge of the olefin diisocyanate mixture worked up by means of crystallization can be reduced or completely avoided.

The inventors of the present invention have surprisingly found that this is possible through the use of specific carboxylic acid esters of the present invention.

Although WO 2017097729 Al already describes the general use of esters of monobasic or polybasic carboxylic acids for flexible polyurethane foams based on polyethercarbonate polyols, the specific carboxylic acid esters of the present invention are not disclosed. Furthermore, it is not apparent to the person skilled in the art from this publication that the use of esters of monobasic or polybasic carboxylic acids can be used to reduce or completely eliminate the charge of the olefin diisocyanate worked up by crystallization. This document merely teaches that through the use of Esters mono- or polybasic carboxylic acids foams can be obtained with a reduced emission of cyclic propylene carbonate

The object of the present invention is achieved by a process for producing flexible polyurethane foams by reacting

Component A) comprising polyether carbonate polyol Al and optionally one or more polyether polyols, where the polyether polyols A2 are free from carbonate units, component B):

Bl) catalysts, and optionally

B2) auxiliaries and additives

C) water and / or physical blowing agents,

With

D) di- and / or polyisocyanates,

the production takes place at a ratio of 90 to 125,

characterized in that the preparation is carried out in the presence of at least one compound E which has the following formula (I):

in which

R ^{1 is} an aromatic hydrocarbon radical having at least 5 carbon atoms or a linear, branched, substituted or unsubstituted aliphatic carbon which is ersto ffrest with at least 2 or in the case of branched at least 3 carbon atoms;

R ^{2 is} a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical; and

n is 1 to 3.

If it is stated in the present invention that a particular compound or radical may be substituted, then substituents known to the person skilled in the art are used. It is particularly preferred that one or more hydrogen atoms in the compounds by -F, -CI, -Br, -I, -OH, = 0, -OR ³ , -OC (= 0) R ³ , -C (= 0 ) R ³ , -NH ₂ , -NHR ³ , -NR ³ _{2 are} replaced, wherein R ^{3 represents} a linear alkyl radical having 1 to 10 carbon atoms or a branched alkyl radical having 3 to 10 carbon atoms. Particularly preferred are the substituents -F, -CI, -OR ³ , -Oc (= O) R ³ , and -C (= O) -R ³ , wherein R ^{3 is} a linear alkyl radical having 1 to 10 carbon atoms or a branched alkyl radical having 3 to 10 carbon atoms represents.

In particular, the present invention relates to:

1. A process for the production of flexible polyurethane foams by reaction of

Component A) comprising polyether carbonate polyol Al, in particular having a Hydro xylzahl according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 120 mg KOH / g (component Al) and optionally one or more polyether polyols, in particular having a hydroxyl value according to DIN 53240-1: 2013-06 from 20 mg KOH / g to 250 mg KOH / g and a content of ethylene oxide from 0 to 60 wt.%

(Component A2), wherein the polyether polyols A2 are free from carbonate units, component B):

Bl) catalysts, and optionally

B2) auxiliaries and additives

C) water and / or physical blowing agents,

With

D) di- and / or polyisocyanates which are 2,4-tolylene diisocyanate and 2,6-

Contain or consist of oluylene diisocyanate;

the production takes place at a ratio of 90 to 125,

characterized in that the preparation in the presence of at least one

Compound E, which has the following formula (I):

in which

R ^{1 is} an aromatic hydrocarbon radical having at least 5 carbon atoms or a linear, branched, substituted or unsubstituted aliphatic radical

Hydrocarbon radical having at least 2, in the case of branched at least 3, carbon atoms;

n is 1 to 3.

2. Method according to aspect 1, characterized in that in formula (I) R ^{1 is} an aromatic hydrocarbon radical having at least 6 carbon atoms or a linear, branched, substituted or unsubstituted aliphatic carbon which is first radical having at least 3, preferably 3 to 10, carbon atoms;

R ^{2 is} a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical having at least 3, preferably 3 to 16, carbon atoms; and n is 1 to 3;

R ¹ is preferably an aromatic hydrocarbon which is first radical having 6 carbon atoms or a linear, branched, substituted or unsubstituted aliphatic saturated hydrocarbon radical having at least 3, preferably 3 to 10, carbon atoms;

more preferably, the compound is an ester of an optionally substituted C 3-12 monocarboxylic acid which has been esterified with a linear or branched C 3-16 alkylalcohol, especially hexylhexanoate;

or an ester of an optionally substituted C _4-12 , more preferably cocooro, dicarboxylic acid which has been esterified with a linear or branched C _3-16 alkyl alcohol, in particular selected from bis (2-ethylhexyl) adipate and diisodecyl sebacate; or an ester of an optionally substituted C5- _16, more preferably Ce-io; Tricarboxylic acid esterified with a linear or branched C 3-16 alkyl alcohol, in particular selected from tris (2-ethylhexyl) O-acetyl citrate, and tributyl O-acetyl citrate;

or an ester of a mono-, di- or tri-substituted benzene having a carboxylic acid group which has been esterified with a linear or branched C 3-16 alkyl alcohol, in particular esters of Ce-16 alkyl alcohols and trimesic acid or trimellitic acid, particularly preferably tris (2) ethylhexyl) trimellitate.

Process according to aspect 1 or 2, characterized in that component A has the following composition:

Al 40 to 100 parts by weight of one or more polyether carbonate polyols having a hydroxyl number according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 120 mg KOH / g,

A2 is 0 to 60 parts by weight of one or more polyether polyols having a

Hydroxyl number according to DIN 53240-1: 2013-06 from 20 mg KOH / g to 250 mg KOH / g and a content of ethylene oxide of 0.10 to 59.0 wt .-%, preferably 1 to 30 wt .-%, stronger preferably 5 to 15 wt .-% and / or a content of propylene oxide from 40 to 99.9 wt .-%, preferably 70 to 99 wt .-%, more preferably 85 to 95 wt -.%, Wherein the polyether polyols A2 free of carbonate units are,

A3 0 to 20 parts by wt., Preferably 0.1 to 10 parts by wt., Based on the sum of the parts by wt. Of the components Al and A2, one or more polyether polyol with a Hydro xylzahl according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 250 mg KOH / g, and a content of ethylene oxide of at least 60 wt .-%, wherein the polyether polyols A3 are free of carbonate units,

A4 from 0 to 40 parts by weight, preferably from 0.1 to 30 parts by weight, based on the sum of the parts by weight of the components A1 and A2, of one or more polymer polyols, PHD polyols and / or PIPA polyols,

A5 0 to 40 parts by wt., Preferably 0.1 to 25 parts by wt., Based on the sum of the parts by wt. Of the components Al and A2, polyols, which do not fall under the definition of the components A1 to A4, where all parts by weight of the components Al, A2, A3, A4, A5 are normalized such that the sum of parts by weight gives Al + A2 in the composition 100.

Method according to one of the preceding aspects, characterized in that the at least one compound E is used in an amount of 1.0 to 15.0, preferably 2.5 to 10.0, more preferably 5 to 8, parts by wt. wherein all parts by weight of the compound E relate to the sum of the parts by weight of the components Al + A2 = 100 parts by weight.

Method according to one of the preceding aspects, characterized in that as component B

Bl catalysts like

a) aliphatic tertiary amines, cycloaliphatic tertiary amines, aliphatic amino, cycloaliphatic amino, aliphatic amidines, cycloaliphatic amidines, urea and derivatives of urea and / or

b) tin (II) salts of carboxylic acids, and

B2 optionally adjuvants and additives are used.

Method according to one of the preceding aspects, characterized in that component A comprises:

Al 65 to 75 parts by weight of one or more polyether carbonate polyols having a hydroxyl number according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 120 mg KOH / g, and A2 35 to 25 parts by weight of one or more polyether polyols with a hydroxyl number according to DIN 53240 of 20 mg KOH / g to 250 mg KOH / g and a content of ethylene oxide of 0.10 to 59.0 wt .-%, preferably 1 to 30 wt .-%, more preferably 5 to 15 Wt .-% and / or a content of propylene oxide from 40 to 99.9 % By weight, preferably 70 to 99% by weight, more preferably 85 to 95% by weight, wherein the polyether polyols A2 are free from carbonate units.

A process according to any of the preceding aspects, characterized in that component Al comprises a polyethercarbonate polyol obtainable by copolymerization of carbon dioxide, one or more alkylene oxides, in the presence of one or more H-functional starter molecules, the polyethercarbonate polyol preferably having a CCk content of 15 to 25 wt .-% has.

Process according to one of the preceding aspects, characterized in that component D comprises at least 50% by weight, preferably at least 80% by weight, of 2,4-tolylene diisocyanate and 2,6-oluylene diisocyanate.

Process according to one of the preceding aspects, characterized in that in the component D at most 21.5 wt .-% of 2,6-tolylene diisocyanate are present, based on the total weight of the component D, preferably wherein 18.5 to 21.5 wt based on the total weight of component D, more preferably wherein 20.0 to 21.5 wt .-% of 2,6-T oluylendiisocyanat contained, based on the total weight of Component D, most preferably containing 20.0% by weight of 2,6-tolylene diisocyanate, based on the total weight of component D. Process according to aspect 9, characterized in that 2,4-tolylene diisocyanate and 2,6- Toluylene diisocyanate as a mixture of at least one batch, preferably two different batches are used, wherein the first batch of 2,4-T oluylendiisocyanat to 2,6-tolylene diisocyanate in the ratio of 80 wt .-% to 20 wt .-% and the second Charge 2,4-toluene lendiisocyanat to 2,6-toluene diisocyanate in the ratio of 67 wt .-% to 33 wt .-%, wherein the proportion of the second batch at most 25 wt .-%, preferably at most 10 wt .-%, based on the total weight of first and second batches, more preferably wherein only the two batches are used as component D. Flexible polyurethane foams obtainable by a process according to any one of aspects 1 to 10. Flexible polyurethane foams according to aspect 11, characterized in that they are open-cell flexible polyurethane foams. Flexible polyurethane foams according to aspect 11 or 12, characterized in that the flexible polyurethane foams have a density according to DIN ISO 845: 2009-

10 from 45.5 to 60.0 kg / m ³ , preferably 46.0 to 58.0 kg / m ³ . Use of the flexible polyurethane foams according to one of the aspects 11 to 13 for the production of furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges, foam films for use in

Automotive parts such as headliners, door panels,

Seat covers and components. Two-component system for the production of flexible polyurethane foams containing

a first component K1 comprising or consisting of:

Component A) comprising polyethercarbonate polyol, in particular having a Hydro xylzahl according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 120 mg KOH / g (component Al) and optionally one or more polyether polyols, in particular having a hydroxyl number according to DIN 53240 -1: 2013-06 from 20 mg KOH / g to 250 mg KOH / g and an ethylene oxide content of 0 to 60% by weight (component A2), where the polyether polyols A2 are free from carbonate units,

B) if necessary

Bl) catalysts, and / or

B2) auxiliaries and additives

C) water and / or physical blowing agents, and

E) a compound having the following formula (I):

in which

R ^{1 is} an aromatic hydrocarbon radical having at least 5 carbon atoms or is a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical having at least 2 carbon atoms; R ^{2 is} a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical; and

n is 1 to 3

and a second component K2 comprising or consisting of:

D) diisocyanates and / or polyisocyanates which contain 2,4-tolylene diisocyanate and 2,6-

Contain or consist of olefin diisocyanate

and at least one catalyst, wherein the component Kl and the component K2 are present in a ratio of an iso cy anate index of 90 to 125 to each other.

If it is disclosed below that it is the hydroxyl number according to DIN 53240, this is understood in particular to mean the hydroxyl number according to DIN 53240-1: 2013-06.

Another aspect of the invention is a process for producing flexible polyurethane foams by reacting

Al> 40 to <100 parts by weight, preferably> 60 to <100 parts by wt., Particularly preferably> 80 to <100 parts by weight of one or more polyether carbonate polyols having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <120 mg KOH / g,

A2 <60 to> 0 parts by weight, preferably <40 to> 0.1 parts by weight, more preferably <20 to> 5 parts by weight of one or more polyether polyols having a hydroxyl value according to DIN

53240 from> 20 mg KOH / g to <250 mg KOH / g and an ethylene oxide content of from 0.10 to 59.0% by weight, preferably from 1 to 30% by weight, more preferably from 5 to 15% by weight. % and / or a content of propylene oxide of 40 to 99.9 wt .-%, preferably 70 to 99 wt .-%, more preferably 85 to 95 wt -.%, wherein the polyether polyols A2 are free of carbonate units, A3 <20 to> 0 parts by weight, preferably 0.1 to 10 parts by weight, based on the sum of parts by weight of components Al and A2, of one or more polyether polyols having a hydroxyl number according to DIN 53240> 20 mg KOH / g to <250 mg KOH / g, and a content of ethylene oxide of> 60 wt .-%, wherein the polyether polyols A3 are free of carbonate units, A4 <40 to> 0 parts by weight, preferably 0.1 to 10 wt -. Parts, based on the sum of the parts by weight of the components Al and A2, of one or more polymer polyols, PHD polyols and / or PIPA polyols,

A5 <40 to> 0 parts by weight, preferably 0.1 to 10 parts by weight, based on the sum of the parts by weight of the components Al and A2, polyols which do not fall within the definition of the components A1 to A4 .

B if necessary

Bl) catalysts and / or B2) auxiliaries and additives

C water and / or physical blowing agents,

With

D di and / or polyisocyanates,

the production takes place at a ratio of> 90 to <120,

wherein all parts by weight of the components Al, A2, A3, A4, A5 are normalized such that the sum of the parts by weight gives Al + A2 in the composition 100,

characterized in that the preparation takes place in the presence of component K.

The components A1 to A5 each refer to "one or more" of said compounds. When using several compounds of a component, the quantity corresponds to the sum of the parts by weight of the compounds.

In a preferred embodiment, component A contains

Al> 65 to <75 parts by wt., Most preferably> 68 to <72 wt. Parts of one or more Polyethercarbonatpolyole having a Hydro xylzahl according to DIN 53240 of> 20 mg KOH / g to <120 mg KOH / g and preferably one C02 content of 15 to 25 wt .-%, and

A2 <35 to> 25 parts by wt., Most preferably <32 to> 28 wt. Parts of one or more polyether polyols having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <250 mg KOH / g and a content of Ethylene oxide from 0.10 to 59.0 wt .-%, preferably 1 to 30 wt .-%, more preferably 5 to 15 wt .-% and / or a content of propylene oxide from 40 to 99.9 wt .-%, preferably from 70 to 99% by weight, more preferably from 85 to 95% by weight, the polyether polyols A2 being free from carbonate units,

wherein component A is preferably free of component A3 and / or A4.

In another embodiment, component A comprises

Al> 65 to <75 parts by wt., Preferably> 68 to <72 wt. Parts of one or more Polyethercarbonatpolyole having a hydroxyl value according to DIN 53240 of> 20 mg KOH / g to <120 mg KOH / g and preferably a CO 2 Content of 15 to 25 wt .-%, and

A2 <35 to> 25 parts by wt., Preferably <32 to> 28 wt. Parts of one or more polyether polyols having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <250 mg KOH / g and a content of ethylene oxide from 0.10 to 59.0% by weight, preferably from 1 to 30% by weight, more preferably from 5 to 15% by weight, and / or from 40 to 99.9% by weight of propylene oxide is preferred From 70 to 99% by weight, more preferably from 85 to 95% by weight, the polyether polyols A2 being free from carbonate units, A3 <20 to> 2 parts by wt., Preferably <10 to> 2 wt. Parts, based on the sum of the parts by wt. Of components Al and A2, of one or more polyether polyols having a hydroxyl number according to DIN 53240> 20 mg KOH / g to <250 mg KOH / g, and a content of ethylene oxide of> 60 wt .-%, wherein the polyether polyols A3 are free of carbonate units, wherein the component A is preferably free of component A4.

In another embodiment, component A comprises

Al> 40 to <100 parts by weight, preferably> 60 to <100 parts by weight, more preferably> 80 to <100 parts by weight, most preferably> 65 to <75 parts by weight of one or more Polyethercarbonatpolyole with a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <120 mg KOH / g and preferably a CO 2 content of 15 to 25 wt .-%, and

A2 <60 to> 0 parts by weight, preferably <40 to> 0 parts by weight, more preferably <20 to> 0 parts by weight, most preferably <35 to> 25 parts by weight of one or more polyether polyols a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <250 mg KOH / g and a content of ethylene oxide of 0.10 to 59.0 wt .-%, preferably 1 to 30% by weight, more preferably 5 to 15 wt .-% and / or a content of propylene oxide from 40 to 99.9 wt .-%, preferably 70 to 99 wt .-%, more preferably 85 to 95 wt -.%, Wherein the polyether polyols A2 are free of carbonate .

A4 <40 to> 0.01 parts by weight, preferably <20 to> 0.01 parts by weight, more preferably <20 to> 1 parts by weight, most preferably <20 to> 2 parts by weight, based on the sum of the parts by weight of the components Al and A2, one or more polymer polyols, PHD polyols and / or PIPA polyols,

A5 <40 to> 0 parts by weight, preferably <20 to> 0.01 parts by weight, based on the sum of the parts by weight of the components Al and A2, of polyols which are not covered by the definition of the components Al to A4 fall, wherein the component A is preferably free of component A3. The specified ranges and preferred ranges of the components A1, A2, A4 and A5 are freely combinable with one another.

The components used in the process according to the invention are described in more detail below.

Component Al

The component Al comprises a polyethercarbonate polyol having a preferred hydroxyl number (OH number) according to DIN 53240-1: 2013-06 of> 20 mg KOH / g to <120 mg KOH / g, preferably from> 20 mg KOH / g to <100 mg KOH / g, more preferably> 25 mg KOH / g to <90 mg KOH / g, which can be obtained by copolymerization of carbon dioxide, one or more alkylene oxides, in the presence of one or more H-functional starter molecules, the polyethercarbonate polyol preferably having a CO 2 content of from 15 to 25% by weight. % having. Preferably, component Al comprises a polyethercarbonate polyol which is obtainable by copolymerization of> 2% by weight to <30% by weight of carbon dioxide and> 70% by weight to <98% by weight of one or more alkylene oxides, in the presence of one or more a plurality of H-functional starter molecules having an average functionality of> 1 to <6, preferably from> 1 to <4, particularly preferably from> 2 to <3. By "H-functional" is meant in the context of the invention, a starter compound opposite Alkoxylation has active H atoms.

Preferably, the copolymerization of carbon dioxide and one or more alkylene oxides takes place in the presence of at least one DMC catalyst (double metal cyanide catalyst).

Preferably, the polyether carbonate polyols used according to the invention also have ether groups between the carbonate groups, which is shown schematically in formula (II). In the scheme according to formula (II) R is an organic radical such as alkyl, alkylaryl or aryl, which may also contain heteroatoms such as O, S, Si, etc., e and f are an integer number. The polyethercarbonate polyol shown in the scheme according to formula (II) should only be understood as meaning that blocks having the structure shown can in principle be found in the polyethercarbonate polyol, but the order, number and length of the blocks can vary and not to that shown in formula (II) Polyethercarbonatepolyol is limited. With respect to formula (II), this means that the ratio of e / f is preferably from 2: 1 to 1:20, more preferably from 1.5: 1 to 1:10.

The proportion of incorporated CO2 ("units derived from carbon dioxide", "CCh content") in a polyether carbonate polyol can be determined from the evaluation of characteristic signals in the 'H-NMR spectrum. The following example illustrates the determination of the proportion carbon dioxide-derived units in a COz / propylene oxide polyethercarbonate polyol started on 1,8-octanediol.

The proportion of incorporated CO in a polyethercarbonate polyol and the ratio of propylene carbonate to polyethercarbonate polyol can be determined by means of 1H-NMR (a suitable device is from Bruker, DPX 400, 400 MHz, pulse program zg30, waiting time dl: 10 s, 64 scans). Each sample is dissolved in deuterated chloroform. The relevant resonances in 1H NMR (relative to TMS = 0 ppm) are as follows:

Cyclic propylene carbonate (which was by-produced) with resonance at 4.5 ppm; Carbonate resulting from carbon dioxide incorporated in the polyethercarbonate polyol having resonances at 5.1 to 4.8 ppm; unreacted propylene oxide (PO) with resonance at 2.4 ppm; Polyether polyol (i.e., without incorporated carbon dioxide) having resonances at 1.2 to 1.0 ppm; as a starter molecule (if present) built 1.8 octanediol with a resonance at 1.6 to 1.52 ppm.

The weight fraction (in% by weight) of polymer-bound carbonate (LC ') in the reaction mixture was calculated according to formula (III),

where the value for N ("denominator" N) is calculated according to formula (IV):

N = [F (5,1-4,8) -F (4,5)] * 102 + F (4,5) * 102 + F (2,4) * 58 + 0,33 * F (l, 2 - 1.0) * 58 + 0.25 * F (l, 6 - 1.52) * 146 (IV)

The following abbreviations apply:

F (4,5) = area of resonance at 4.5 ppm for cyclic carbonate (equivalent to one atom of H) F (5, l-4,8) = area of resonance at 5, 1-4, 8 ppm for polyethercarbonate polyol and a H atom for cyclic carbonate.

F (2,4) = area of resonance at 2.4 ppm for free, unreacted PO

F (l, 2-1,0) = area of resonance at 1, 2-1.0 ppm for polyether polyol

F (1, 6-1, 52) = area of resonance at 1.6 to 1.52 ppm for 1.8 octanediol (starter), if any.

The factor 102 results from the sum of the molar masses of CO2 (molar mass 44 g / mol) and that of propylene oxide (molar mass 58 g / mol), the factor 58 results from the molar mass of propylene oxide and the factor 146 results from the molar mass of the initiator used 1,8-octanediol (if present). The weight fraction (in% by weight) of cyclic carbonate (CC ') in the reaction mixture was calculated according to formula (V),

F (4,5) * 102

CC * 100%

N (V) where the value of N is calculated according to formula (IV).

From the values of the composition of the reaction mixture, the composition based on the polymer portion (consisting of polyether polyol, which was composed of starter and propylene oxide during the activation steps taking place under CCh-free conditions, and polyether carbonate polyol, composed of starter, propylene oxide and carbon dioxide during to calculate the activation steps taking place in the presence of CO2 and during the copolymerization), the non-polymer constituents of the reaction mixture (ie cyclic propylene carbonate and optionally present, unreacted propylene oxide) were eliminated by calculation. The weight fraction of the carbonate repeat units in the polyethercarbonate polyol was converted to a weight fraction of carbon dioxide by the factor F = 44 / (44 + 58). The specification of the CCF content in the polyethercarbonate polyol is normalized to the proportion of the polyethercarbonate polyol molecule formed in the copolymerization and, if appropriate, the activation steps in the presence of CO ₂ (ie the proportion of the polyethercarbonatepolyol molecule which originates from the initiator (1, 8-octanediol, if any) as well as resulting from the reaction of the initiator with epoxide added under CCE-free conditions was not considered).

For example, the preparation of polyethercarbonate polyols according to Al involves:

(O) an H-functional initiator compound or a mixture of at least two H-functional starter compounds presented and optionally water and / or other volatile compounds by elevated temperature and / or reduced pressure are removed ("drying"), wherein the DMC catalyst the H-functional initiator compound or the mixture of at least two H-functional starter compounds is added before or after drying,

(ß) for the activation of a partial amount (based on the total amount used in the activation and copolymerization of alkylene oxides) of one or more alkylene oxides to the mixture resulting from step (a) is added, wherein this addition of a partial amount of alkylene oxide, optionally in the presence of CO2, and then occurring due to the following exothermic chemical reaction Temperature peak ("hotspot") and / or a pressure drop in the reactor is respectively waiting, and wherein the step (ß) for activation can also be multiple times,

(g) one or more of the alkylene oxides and carbon dioxide are added to the mixture resulting from step (β), wherein the alkylene oxides used in step (β) may be the same or different from the alkylene oxides used in step (g).

In general, it is possible to use Al alkylene oxides (epoxides) having 2 to 24 carbon atoms for preparing the polyether carbonate polyols. The alkylene oxides having 2 to 24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide, 2,3-pentene oxide, 2-methyl-1, 2-butene oxide, 3-methyl-l, 2-butene oxide, 1 -hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl - 1, 2-pentenoxide, 4-methyl-1, 2-pentenoxide, 2-ethyl-l, 2-butene oxide, 1-epoxide, 1 - octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecenoxide, 1 -dodecenoxid , 4-methyl-1,2-pentenoxide, butadiene monoxide, isoprene monoxide, cyclopentene oxide, cyclohexene oxide, cycloheptenoxide, cyclooctene oxide, styrene oxide, methylstyrene oxide, pinene oxide, mono- or multiply epoxidized fats as mono-, di- and triglycerides, epoxidized fatty acids, Cl-C24 Esters of epoxidized fatty acids, epichlorohydrin, glycidol, and derivatives of glycidol, such as methyl glycidyl ether, ethyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl ether, glycidyl methacrylate, and epoxy functional alkoxysilanes such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, 3-glycidyloxypropyltriisopropoxysilane. The alkylene oxides used are preferably ethylene oxide and / or propylene oxide and / or 1,2-butylene oxide, particularly preferably propylene oxide.

In a preferred embodiment of the invention, the proportion of ethylene oxide in the total amount of propylene oxide and ethylene oxide used is> 0 and <90 wt .-%, preferably> 0 and <50 wt .-% and particularly preferably free of ethylene oxide.

As a suitable H-functional starting compound, compounds having active for the alkoxylation H atoms can be used. For the alkoxylation active groups having active H atoms are, for example, -OH, -NH 2 (primary amines), -NH- (secondary amines), -SH and -CO ₂ H, preferred are -OH and -NH ₂ , more preferably -OH , As H-functional starter compound, for example, one or more compounds selected from the group consisting of water, monohydric or polyhydric alcohols, polyhydric amines, polyhydric thiols, aminoalcohols, thioalcohols, hydroxyesters, polyetherpolyols, polyesterpolyols, polyesteretherpolyols, polyethercarbonatepolyols, polycarbonatepolyols, polycarbonates, polyethylenimines, polyetheramines (eg so-called Jeffamine® from Huntsman, such as D-230, D-400, D- 2000, T-403, T-3000, T-5000 or corresponding products from BASF, such as, for example, polyetheramine D230, D400, D200, T403, T5000), polytetrahydro-hydroxides (for example BASF's PolyTHF®, such as, for example, US Pat. PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800, 2000), polytetrahydrofuranamines (BASF product polytetrahydrofuranamine 1700), polyether thiols, polyacrylate polyols, castor oil, the mono- or diglyceride of ricinoleic acid, monoglycerides of fatty acids, chemically modified mono-, Di- and / or triglycerides of fatty acids, and C1-C24 alkyl-F ettsäureester containing on average at least 2 OFI groups per molecule used. By way of example, the C1-C24 alkyl fatty acid esters which contain on average at least 2 OFI groups per molecule are commercial products such as Lupranol Balance® (BASF AG), Merginol® types (Hobum Oleochemicals GmbH) , Sovermol® types (Cognis Germany GmbH & Co. KG) and Soyol®TM types (USSC Co.).

Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter compounds. As monofunctional alcohols can be used: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl 3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-t-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3 Pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, phenol, 2-hydroxybiphenyl, 3 -Hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine. Suitable monofunctional amines are: butylamine, t-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine. As monofunctional thiols can be used: ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 3-methyl-1-butanethiol, 2-butene-1-thiol, thiophenol. As monofunctional carboxylic acids may be mentioned: formic acid, acetic acid, propionic acid, butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.

Polyhydric alcohols suitable as H-functional starter compounds are, for example, dihydric alcohols (for example ethylene glycol, diethyl glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1, 5-pentanediol, methylpentanediols (such as, for example, 3-methyl-1,5-pentanediol), 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis (hydroxymethyl) cyclohexanes (such as, for example, 1,4-bis (hydroxymethyl) cyclohexane), Triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol,

Tripropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols); trihydric alcohols (such as, for example, trimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil); tetrahydric alcohols (such as pentaerythritol); Polyalcohols (such as sorbitol, hexitol, sucrose, starch, starch hydrolysates, cellulose, cellulose hydrolysates, hydroxy-functionalized fats and oils, in particular castor oil), as well as all modification products of these aforementioned alcohols with different amounts of e-caprolactone. In mixtures of H-functional initiators, it is also possible to use trihydric alcohols, for example trimethylolpropane, glycerol, trishydroxyethyl isocyanurate and castor oil.

The H-functional starter compounds may also be selected from the class of polyether polyols, in particular those having a molecular weight Mn in the range of 100 to 4000 g / mol, preferably 250 to 2000 g / mol. Preference is given to polyether polyols which are composed of repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% propylene oxide units, more preferably with a proportion of 50 to 100% propylene oxide units. These may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide. Suitable polyether polyols composed of repeating propylene oxide and / or ethylene oxide units are, for example, the Desmophen®, Acclaim®, Arcol®, Baycoll®, Bayfill®, Bayflex® Baygal®, PET® and polyether polyols Covestro Deutschland AG (such as Desmophen® 3600Z, Desmophen® 1900U, Acclaim® Polyol 2200, Acclaim® Polyol 40001, Arcol® Polyol 1004, Arcol® Polyol 1010, Arcol® Polyol 1030, Arcol® Polyol 1070, Baycoll® BD 1110, Bayfill® VPPU 0789, Baygal® K55, PET® 1004, Polyether® S180). Further suitable homo-polyethylene oxides are, for example, the Pluriol® E grades from BASF SE, suitable homopolypropylene oxides are, for example, the Pluriol® P grades from BASF SE, suitable mixed copolymers of ethylene oxide and propylene oxide are, for example, Pluronic® PE or Pluriol® RPE - Trademarks of BASF SE.

The H-functional starter compounds may also be selected from the class of substances of the polyesterpolyols, in particular those having a molecular weight Mn in the range from 200 to 4500 g / mol, preferably from 400 to 2500 g / mol. Polyester polyols used are at least difunctional polyesters. Polyester polyols preferably consist of alternating acid and alcohol units. As acid components z. For example, succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, Phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid,

T etrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of said acids and / or anhydrides used. As alcohol components z. B. ethanediol, 1, 2-propanediol, 1,3-propanediol, 1, 4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis (hydroxymethyl) cyclohexane, diethylene glycol, Dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures of the alcohols mentioned. If divalent or polyhydric polyether polyols are used as the alcohol component, polyester polyethers are obtained which can likewise serve as starter compounds for the preparation of the polyether carbonate polyols. If polyether polyols are used to prepare the polyester ether polyols, polyether polyols having a number average molecular weight Mn of 150 to 2000 g / mol are preferred.

Furthermore, as H-functional starter compounds polycarbonate polyols (such as polycarbonate diols) can be used, in particular those having a molecular weight Mn in the range of 150 to 4500 g / mol, preferably 500 to 2500, for example by reacting phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and di- and / or polyfunctional alcohols or polyester polyols or polyether polyols. Examples of polycarbonate polyols are found, for. As in EP-A 1359177. For example, as the polycarbonate diols Desmophen® C types of Covestro Germany AG can be used, such as. Desmophen® C 1100 or Desmophen® C 2200.

Likewise, polyethercarbonate polyols can be used as H-functional starter compounds. In particular, polyether carbonate polyols prepared by the method described above are used. These polyether carbonate polyols used as H-functional starter compounds are previously prepared in a separate reaction step.

Preferred H-functional starter compounds are alcohols of the general formula (VIII),

HO- (CH ₂ ) _X -OH (VIII) where x is a number from 1 to 20, preferably an even number from 2 to 20. Examples of alcohols according to formula (VIII) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol. Further preferred H-functional starter compounds are neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, reaction products of the alcohols of the formula (II) with e-caprolactone, for example reaction products of trimethylolpropane with e-caprolactone, reaction products of Glycerol with e-caprolactone, as well as reaction products of pentaerythritol with e-caprolactone. Preference is furthermore given to using water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyether polyols composed of repeating polyalkylene oxide units as H-functional starting compounds.

The H-functional starter compounds are particularly preferably one or more compounds selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and tri-functional polyether polyols, wherein the polyether polyol of a di- or tri-H-functional starter substance and propylene oxide or a di- or tri-H-functional starter substance, propylene oxide and ethylene oxide is constructed. The polyether polyols preferably have a number average molecular weight Mn in the range of 62 to 4500 g / mol and in particular a number average molecular weight Mn in the range of 62 to 3000 g / mol, very particularly preferably a molecular weight of 62 to 1500 g / mol. The polyether polyols preferably have a functionality of> 2 to <3.

In a preferred embodiment of the invention, the polyethercarbonate polyol Al is obtainable by addition of carbon dioxide and alkylene oxides to H-functional starter compounds using multimetal cyanide (DMC) catalysts. The preparation of polyethercarbonate polyols by addition of alkylene oxides and CO.sub.2 to H-functional starter compounds using DMC catalysts is known, for example, from EP-A 0222453, WO-A 2008/013731 and EP-A 2115032.

In principle, DMC catalysts are known from the prior art for the homopolymerization of epoxides (see for example US-A 3 404 109, US-A 3 829 505, US-A 3 941 849 and US-A 5 158 922). DMC catalysts which are described, for example, in US Pat. No. 5,470,813, EP-A 700 949, EP-A 743 093, EP-A 761 708, WO-A 97/40086, WO-A 98/16310 and WO-A 00 No. 4,676,449 have very high activity in the homopolymerization of epoxides and allow the preparation of polyether polyols and / or polyether carbonate polyols at very low catalyst levels (25 ppm or less). A typical example are the highly active DMC catalysts described in EP-A 700 949 which, in addition to a double metal cyanide compound (eg zinc hexacyanocobaltate (III)) and an organic complex ligand (eg tert-butanol), also have a polyether with a number average molecular weight Mn greater than 500 g / mol. The DMC catalyst is usually used in an amount of <1% by weight, preferably in an amount of <0.5% by weight, more preferably in an amount of <500 ppm and in particular in an amount of <300 ppm, each based on the weight of the polyether carbonate used.

In a preferred embodiment of the invention, the polyethercarbonate polyol Al has a content of carbonate groups ("units derived from carbon dioxide"), calculated as CO 2, of> 2.0 and <30.0 wt.%, Preferably of> 5.0 and < 28.0 wt .-% and particularly preferably of> 10.0 and <25.0 wt .-% to.

In a further embodiment of the process according to the invention, the polyether carbonate polyols or polyols have a hydroxyl number of> 20 mg KOH / g to <250 mg KOH / g and are obtainable by copolymerization of> 2.0% by weight to <30.0 Wt .-% carbon dioxide and> 70 wt .-% to <98 wt .-% of propylene oxide in the presence of a hydroxy-functional starter molecule, such as trimethylolpropane and / or glycerol and / or propylene glycol and / or sorbitol. The hydroxyl number can be determined according to DIN 53240.

In a further embodiment, a polyether carbonate polyol Al is used, containing blocks of the formula (II) wherein the ratio e / f of 2: 1 to 1: 20.

In a further embodiment of the invention, component Al is used to 100 parts by weight.

Component A2

Component A2 comprises polyether polyols, preferably having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <250 mg KOH / g, preferably from> 20 to <112 mg KOH / g and more preferably> 20 mg KOH / g to < 80 mg KOH / g and is free of carbonate units. The preparation of the compounds according to A2 can be carried out by catalytic addition of one or more alkylene oxides to H-functional starter compounds.

As alkylene oxides (epoxides) it is possible to use alkylene oxides having 2 to 24 carbon atoms. The alkylene oxides having 2 to 24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butoxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-Pentenoxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl 1, 2-pentenoxide, 4-methyl-1, 2-pentenoxide, 2-ethyl

1,2-butene oxide, 1-epoxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecenoxide, 1-dodecene oxide, 4-methyl-1, 2-pentenoxide, butadiene monoxide, isoprene monoxide, cyclopentene oxide, cyclohexene oxide, cycloheptenoxide, cyclooctene oxide, Styrene oxide, methyl styrene oxide, pinene oxide, mono- or poly-epoxidized fats as mono-, di- and triglycerides, epoxidized fatty acids, C 1 -C 24 esters of epoxidized fatty acids, epichlorohydrin, glycidol, and derivatives of glycidol, such as methyl glycidyl ether, ethyl glycidyl ether, 2 Ethylhexyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate and epoxy-functional alkyoxysilanes, such as, for example, 3-glycidyloxypropyltrimethoxysilane, 3

Glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, 3

Glycidyloxypropyltrlisopropoxysilan. The alkylene oxides used are preferably ethylene oxide and / or propylene oxide and / or 1,2-butylene oxide. Particularly preferably, an excess of propylene oxide and / or 1, 2-butylene oxide is used. The alkylene oxides can be added to the reaction mixture individually, in a mixture or in succession. They may be random or block copolymers. If the alkylene oxides are metered in succession, the products produced (polyether polyols) contain polyether chains with block structures.

The H-functional starter compounds have functionalities of> 2 to <6 and are preferably hydroxy-functional (OH-functional). Examples of hydroxy-functional starter compounds are propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol,

1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol, 3-methyl-1,5-pentanediol, 1,12-dodecanediol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, Catechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, methylol group-containing condensates of formaldehyde and phenol or melamine or urea. These can also be used in mixture. Preferably is used as starter compound 1, 2-propylene glycol and / or glycerol and / or T rimethylolpropan and / or sorbitol.

The polyether polyols according to A2 have a content of> 0.1 to <59.0 wt .-%, preferably from> 1 to <30 wt .-%, more preferably> 5 to <15 wt .-% of ethylene oxide and / or a content of 40 to 99.9 wt .-%, preferably 70 to 99 wt .-%, more preferably 85 to 95 wt -.% Of propylene oxide. Particularly preferably, the propylene oxide units are terminal.

Component A3

Component A3 comprises polyether polyols having a hydroxyl number according to DIN 53240> 20 mg KOH / g to <250 mg KOH / g, preferably from> 20 to <112 mg KOH / g and more preferably> 20 mg KOH / g to <80 mg KOH / g.

The preparation of component A3 is in principle analogous to that of component A2, but with a content of ethylene oxide in the polyether polyol of> 60 wt .-%, preferably> 65% by weight is set.

Suitable alkylene oxides and H-functional starter compounds are the same as described for component A2.

As H-functional starter compounds, however, preference is given to those which have a functionality of> 3 to <6, more preferably of 3, so that polyether triols are formed. Preferred starter compounds having a functionality of 3 are glycerol and / or trimethylolpropane, particularly preferred is glycerol.

In a preferred embodiment, the component A3 is a glycerol-started tri functional polyether having an ethylene oxide content of 68 to 73 wt .-% and an OH number of 35 to 40 mg KOH / g.

Component A4

Component A4 includes polymer polyols, PHD polyols, and PIPA polyols. Polymer polyols are polyols that are more suitable for free radical polymerization Monomers such as styrene or acrylonitrile in a base polyol, such as a polyether polyol and / or Polyethercabonatpolyol generated solid polymers.

PHD (polyurea dispersion) polyols are prepared, for example, by in situ poly merization of an isocyanate or an isocyanate mixture with a diamine and / or hydrazine in a polyol, preferably a polyether polyol. The PHD dispersion is preferably prepared by reacting an isocyanate mixture used from a mixture of 75 to 85% by weight of 2,4-tolylene diisocyanate (2,4-TDI) and 15 to 25% by weight of 2,6-T oluylene diisocyanate (2,6-TDI) with a diamine and / or hydrazine in a polyether polyol, preferably a polyether polyol and / or polyether carbonate polyol, prepared by alkoxylation of a tri functional starter (such as glycerol and / or trimethylolpropane), in the case of the polyethercarbonate polyol in the presence of carbon dioxide. Methods of making PHD dispersions are described, for example, in US 4,089,835 and US 4,260,530.

The PIPA polyols are polyisocyanate polyaddition with alkanolamine-modified, preferably triethanolamine-modified polyether polyols and / or polyether carbonate polyols, the polyether (carbonate) polyol having a functionality of from 2.5 to 4 and a hydroxyl number of> 3 mg KOH / g to <112 mg KOH / g (molecular weight 500 to 18000). Preferably, the polyether polyol is "EO capped", i. the polyether polyol has terminal ethylene oxide groups. PIPA polyols are described in detail in GB 2 072 204 A, DE 31 03 757 A1 and US 4,374,209 A.

Component A5

As component A5, it is possible to use all polyhydroxy compounds known to the person skilled in the art which do not fall under the definition of the components A1 to A4, and preferably have an average OH functionality of> 1.5.

These can be, for example, low molecular weight diols (for example 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (for example glycerol, trimethylolpropane) and tetraoxyde (for example pentaerythritol), polyesterpolyols, polythioetherpolyols or polyacrylatepolyols , as well as polyether polyols or polycarbonate polyols which do not fall under the definition of the components A1 to A4. It is also possible, for example, to use ethylenediamine and triethanolamine-initiated polyethers. These compounds are not among the compounds according to the definition of component B2. Component B

As catalysts according to the component Bl are preferably

a) aliphatic tertiary amines (for example trimethylamine, tetramethylbutanediamine,

Dimethylaminopropylamine, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine), cycloaliphatic tertiary amines (e.g. 1,4-diaza (2,2,2) bicyclooctane), aliphatic amino ethers (e.g. bis-dimethylaminoethyl ether, 2- (2-dimethylaminoethoxy ethanol and N, N, N-trimethyl-N-hydroxyethyl-bisaminoethyl ether), cycloaliphatic amino ethers (for example N-ethylmorpholine), aliphatic amidines, cycloaliphatic amidines, urea and derivatives of urea (such as Aminoalkylhamstoffe, see for example EP-A 0 176 013, in particular (3-dimethylaminopropylamine) urea) and / or

b) Tin (II) salts of carboxylic acids

used.

In particular, the tin (II) salts of carboxylic acids are used, the respective underlying carboxylic acid having from 2 to 24 carbon atoms. For example, as tin (II) salts of carboxylic acids, one or more compounds selected from the group consisting of tin (II) salt of 2-ethylhexanoic acid (ie, stannous (2-ethylhexanoate) or stannous octoate), tin (II ) Salt of 2-butyloctanoic acid, tin (II) salt of 2-hexyldecanoic acid, tin (II) salt of neodecanoic acid, stannous salt of isononanoic acid, stannous salt of oleic acid, tin (II ) Salt of Ricinolsäirre and tin (II) laurate used.

In a preferred embodiment of the invention, at least one tin (II) salt of the formula (IX)

Sn (CxH _{2x + 1} COO) ₂ (IX) used, wherein x is an integer from 8 to 24, preferably 10 to 20, particularly preferably from 12 to 18. Particularly preferred in formula (IX) is the alkyl chain C _X H _{2X + I of} the carboxylate is a branched carbon chain, ie C _X H _{2X + I} is an iso-alkyl group.

Most preferred as tin (II) salts of carboxylic acids are one or more compounds selected from the group consisting of stannous salt of 2-butyloctanoic acid, i. Tin (II) - (2-butyloctoate), stannous (II) salt of ricinoleic acid, i. Tin (II) trinocinoleate and stannous salt of 2-hexyldecanoic acid, i. Tin (II) - (2-hexyldecanoate) used.

In another preferred embodiment of the invention, the component B1 is Bl.l> 0.05 to <1.5 parts by weight, based on the sum of the parts by weight of the components Al and A2, urea and / or derivatives of urea and Bl.2> 0.03 to <1.5 parts by weight, based on the sum of the parts by weight of the components Al and A2, of other catalysts than those of component Bl.2, wherein the content of amine catalysts in the Component Bl .2 maximum 50 wt .-% based on component Bl may be used.

Component Bl.l comprises urea and derivatives of urea. As derivatives of urea may be mentioned, for example: Aminoalky lhamsto ffe, such as. (3-Dimethylaminopropylamine) - urea and 1, 3 -Bis [3 - (dimethylamino) propyl] urea. It is also possible to use mixtures of urea and urea derivatives. Preference is given to using exclusively urea in component B1.1. The component Bl .l is used in amounts of from> 0.05 to <1.5 parts by weight, preferably from> 0.1 to <0.5 parts by weight, more preferably from> 0.25 to <0, 35 parts by weight, based on the sum of the parts by weight of the components Al to A2 used.

Component Bl .2 is used in amounts of> 0.03 to <1.5 parts by weight, preferably> 0.03 to <0.5 parts by weight, more preferably of> 0.1 to <0.3 Parts by weight, very particularly preferably from> 0.2 to <0.3 parts by weight, based on the sum of the parts by weight of components Al to A2 used.

The content of amine catalysts in component B1.2 is preferably at most 50% by weight, based on component B1.1, more preferably at most 25% by weight, based on component B1.1. Most preferably, component B1. Is free from amine catalysts. As catalysts of component Bl.2, e.g. the tin (II) salts of carboxylic acids described above are used.

As in small amounts (see above) optionally used aminic catalysts may be mentioned: aliphatic tertiary amines (for example, trimethylamine, tetramethylbutandiamin, 3-dimethylaminopropylamine, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamin), cycloaliphatic tertiary amines (for example , 4-diaza (2,2,2) bicyclooctane), aliphatic aminoethers (for example bisdimethylaminoethyl ether, 2- (2-dimethylaminoethoxy) ethanol and N, N, N-trimethyl-N-hydroxyethyl-bisaminoethylether), cycloaliphatic aminoethers (for example N- Ethylmorpholine), aliphatic amidines and cycloaliphatic amidines.

The "amine catalysts" mentioned in Bl.2 do not include urea or its derivatives. A non-alkaline medium can preferably be achieved by using urea and / or derivatives of urea as catalysts in accordance with component B1, and no amine catalysts are used.

As component B2, auxiliaries and additives can be used, such as

a) surface-active additives, such as emulsifiers and foam stabilizers, in particular those with low emission, such as products of the Tegostab® series b) additives, such as reaction retarders (eg acidic substances such as hydrochloric acid or organic acid halides), cell regulators (such as paraffins or fatty alcohols or dimethylpolysiloxanes) , Pigments, dyes, flame retardants (other than component K3, such as ammonium polyphosphate), other stabilizers against aging and weathering, antioxidants, plasticizers, fungistatic and bacteriostatic substances, fillers (such as barium sulfate, kieselguhr, carbon black or chalk ) and release agents.

These optional auxiliaries and additives are described, for example, in EP-A 0 000 389, pages 18 to 21. Further examples of auxiliaries and additives which may optionally be used according to the invention and details of the use and mode of action of these auxiliaries and additives are described in the Kunststoff-Handbuch, Volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Munich, 3rd edition, 1993 , eg on pages 104-127.

Component C

As component C, water and / or physical blowing agents are used. As physical blowing agents, for example, carbon dioxide and / or volatile organic substances are used as blowing agents. Preferably, water is used as component C.

Component D

The di- and / or polyisocyanates of the present invention contain or consist of 2,4-oluylene diisocyanate and 2,6-toluene diisocyanate. These are, for example, those polyisocyanates as described in EP-A 0 007 502, pages 7-8. As a rule, the technically readily available polyisocyanates, for example the 2,4- and 2,6-T oluylendiisocyanat, and any mixtures of these with isomers ("TDI") are preferred; Polyphenyl polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret-containing polyisocyanates ("modified polyisocyanates"), in particular those modified polyisocyanates which differ from the 2,4- and / or 2,6- Derive tolylene diisocyanate or from 4,4'- and / or 2,4 '-Diphenylmethandiisocyanat. Preferably, a mixture of 2,4- and 2,6-toluene diisocyanate with 4,4'- and / or 2,4'- and / or 2,2'-diphenylmethane diisocyanate and Polyphenylpolymethylenpolyisocyanat ('' multi-core MDI ') is used. Particular preference is given to using 2,4- and / or 2,6-toluene diisocyanate.

In a further embodiment of the process according to the invention, the isocyanate component D comprises 100% 2,4-oluylene diisocyanate.

In a preferred embodiment of the method according to the invention, the ratio is> 90 to <120. Preferably, the ratio is in a range of> 100 to <115, more preferably> 102 to <110. The index (index) indicates the percentage ratio of the actually used Isocyanate amount to stoichiometric, ie for the implementation of OH equivalents calculated amount of isocyanate groups (NCO) amount.

Code = [amount of isocyanate used]: (calculated amount of isocyanate) × 100

(XI)

In a preferred aspect, the components are used as follows:

Component Al in 70 to 100 wt .-%, in particular 90 wt .-% or 100 wt .-%; and / or component A2 in 0 to 30 wt .-%, in particular 10 wt .-% or 0 wt .-%, wherein the sum of the components Al and A2 is 100 wt .-%; and or

Component Bl in 0.02 to 0.8% by weight, preferably 0.06 to 0.25% by weight, particularly preferably 0.22% by weight, based on 100 wt .-% of Al and A2; and or

Component B2 in 0.1 to 6 wt .-%, preferably 0.2 to 1.2 wt .-%, particularly preferably 1.3 wt .-%, based on 100 wt .-% of Al and A2; and or

Component C in 0.8 to 3.0 wt .-%, preferably 1.9 wt .-%, based on 100 wt .-% of Al and A2; and or

Component E in 2.0 wt .-% to 12 wt%, preferably 2, 0 to 8.0 wt .-%, based on 100 wt .-% of Al and A2.

To produce the flexible polyurethane foams, the reaction components are preferably reacted according to the known one-step process, often using mechanical equipment, for example those described in EP-A 355 000 to be discribed. Details of processing equipment which also come into question according to the invention, in Plastics Handbook, Volume VII, published by Vieweg and Höchtlen, Carl Hanser Verlag, Munich 1993, for example, on pages 139 to 265 described. The flexible polyurethane foams can be produced as molded or also as block foams, preferably as slab foams. The invention therefore relates to a process for the preparation of the flexible polyurethane foams, the flexible polyurethane foams produced by these processes, the flexible polyurethane foams or flexible polyurethane foams produced by these processes, which

Use of the flexible polyurethane foams for the production of molded parts and the molded parts themselves.

The flexible polyurethane foams obtainable according to the invention find, for example, the following applications: furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges, foamed films for use in automotive parts such as headliners, door paneling, seat covers and components.

The flexible foams according to the invention preferably have a bulk density according to DIN EN ISO 845: 2009-10 in the range of> 16 to <60 kg / m ³ , preferably> 20 to <50 kg / m ³ .

Examples

Component A:

Al-1 CARDYON® LC05 is a polyol mixture consisting of 70% by weight of DESMOPHEN 95LC04 and 30% by weight of ARCOL POLYOL 1108 with an OH number of 54 mg

KOH / g; C0 ₂ content: approx. 14%; DESMOPHEN 95LC04: polyethercarbonate polyol, glycerol-started; Propylene oxide-based; prepared by DMC catalysis OH number: 56 mg KOH / g. ARCOL POLYOL 1108: propylene oxide / ethylene oxide based polyol; prepared by DMC catalysis; Starter: glycerin; OH number: 48 mg KOH / g

Al-2 DESMOPHEN 41WB01 is a commercially available ethylene oxide / propylene oxide based polyol (Covestro AG) with a very high proportion of ethylene oxide groups; Starter: glycerin; KOH catalysis; OH number of 37 mg KOH / g component B:

Bl-1 Bis [2-dimethylamino) ethyl] ether (70 wt .-%) (wt .-% in dipropylene glycol 30) (Niax ^® Catalyst Al, Momentive Performance Chemicals, Leverkusen, Germany).

Bl -2 1, 4-diazabicyclo [2.2.2] octane (33 wt .-%) in dipropylene glycol (67 wt .-%) (Dabco ^®

33 LV, Evonik, Essen, Germany).

B2-1 polyether-based foam stabilizer T egostab ^® B 8244 (Evonik, Essen, Germany). B2-2 polyether-based foam stabilizer T egostab ^® B 8002 (Evonik,

Essen, Germany).

Component C: Water Component D:

D-l: mixture of 2,4- and 2,6-TDI in the weight ratio 80:20 and with an NCO

Content from 48 to 48.2 wt .-%, commercially available as Desmodur T 80 (Covestro AG).

D-2: mixture of 2,4- and 2,6-TDI in the weight ratio 67:33 and with an NCO

Content of 48-48.2 wt .-%, commercially available as Desmodur T 65 (Covestro AG). Component E:

E-I: diisodecyl sebacate, commercially available as Uniplex DIDS

E-2: Tris (2-ethylhexyl) O-acetyl citrate, commercially available as Citrofol AHII

E-3: bis (2-ethylhexyl) adipate, commercially available as Oxsoft DOA

Production of flexible polyurethane foams

Under the processing conditions customary for the production of flexible polyurethane foams, the starting components are processed in a one-stage process by means of block foaming.

The density was determined according to DIN EN ISO 845: 2009-10.

The compression hardness (CLD 40%) was determined in accordance with DIN EN ISO 3386-1: 2015-10

at a deformation of 40%, 1st or 4th cycle.

The tensile strength and the elongation at break were determined according to

DIN EN ISO 1798: 2008-04.

The compression set (DVR 90%) was determined according to DIN EN ISO 1856: 2008-01 at 90% deformation.

The compression set (DVR 50%) was determined according to DIN EN ISO 1856: 2008-01 (22 h, 70 ° C) at 50% deformation.

In the following table are comparative examples as VBsp. and erfmdungsgemäße examples given as Ex.

Table 1: VBsp. 1 and Ex. 1 to 6, continuation of the table on the next page Ex. 7-12; pphp = parts per 100 parts polyol

Claims

Claims:

A process for producing flexible polyurethane foams by reacting component A) comprising polyethercarbonate polyol Al (component A1) and optionally one or more polyetherpolyols (component A2), the polyetherpolyols A2 being free from carbonate units,

Component B):

Bl) catalysts, and optionally

B2) auxiliaries and additives

C) water and / or physical blowing agents,

With

D) di- and / or polyisocyanates which contain or consist of 2,4-tolylene diisocyanate and 2,6-oluylene diisocyanate;

the production takes place at a ratio of 90 to 125,

in which

R ^{1 is} an aromatic hydrocarbon which is at least 5 carbon atoms or is a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical having at least 2, in the case of branching at least 3, carbon atoms;

n is 1 to 3.

Process according to claim 1, characterized in that in formula (I)

R ^{1 is} an aromatic carbon which is first of all at least 6 carbon atoms or is a linear, branched, substituted or unsubstituted aliphatic carbon which is first-of-origin with at least 3 carbon atoms;

R ^{2 is} a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical having at least 3 carbon atoms; and n is 1 to 3.

Process according to claim 1 or 2, characterized in that component A has the following composition:

A2 0 to 60 parts by weight of one or more polyether polyols having a hydroxyl value according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 250 mg KOH / g and a content of ethylene oxide of 0.1 to 59 wt. %, where the polyether polyols A2 are free from carbonate units,

A3 0 to 20 parts by weight, based on the sum of the parts by weight of the components Al and A2, of one or more polyether polyols having a hydroxyl number according to DIN 53240-1: 2013-06 from 20 mg KOH / g to 250 mg KOH / g, and a content of ethylene oxide of at least 60 wt .-%, wherein the polyether polyols A3 are free of carbonate units,

A4 0 to 40 parts by weight, based on the sum of the parts by weight of the components Al and A2, one or more polymer polyols, PHD polyols and / or PIPA polyols, A5 0 to 40 parts by weight, based on the sum of the parts by weight of the components Al and A2, polyols, which do not fall under the definition of the components Al to A4, wherein all parts by weight of the components Al, A2, A3, A4, A5 are normalized such that the sum of parts by weight Al + Al in the composition gives 100.

Method according to one of the preceding claims, characterized in that the at least one compound E is used in an amount of 1.0 to 15.0 parts by weight, wherein all parts by weight of the compound E on the sum of parts by weight of the components Al + A2 = 100 parts by weight.

Method according to one of the preceding claims, characterized in that as component B

Bl catalysts like

a) aliphatic tertiary amines, cy cloaliphati see tertiary amines, aliphatic amino, cycloaliphatic amino, aliphatic amidines, cycloaliphatic amidines, urea and derivatives of urea and / or

b) tin (II) salts of carboxylic acids, and

B2 optionally adjuvants and additives are used.

6. The method according to any one of the preceding claims, characterized in that component A comprises:

Al 65 to 75 parts by weight of one or more polyether carbonate polyols having a hydroxyl number according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 120 mg KOH / g, and A2 35 to 25 parts by weight of one or more polyether polyols with a hydroxyl number according to DIN 53240 of 20 mg KOH / g to 250 mg KOH / g and a content of ethylene oxide of 0.1 to 59 wt .-%, wherein the polyether polyols A2 are free of carbonate. 7. The method according to any one of the preceding claims, characterized in that component Al comprises a polyethercarbonate polyol which is obtainable by copolymerization of carbon dioxide, one or more alkylene oxides, in the presence of one or more H-functional starter molecules. 8. The method according to any one of the preceding claims, characterized in that component D comprises at least 50 wt .-% 2,4-T oluylendiisocyanat and 2,6-T oluylendiisocyanat.

9. The method according to any one of the preceding claims, characterized in that contained in the component D at most 21.5 wt .-% of 2,6-toluene diisocyanate, based on the total weight of component D.

10. The method according to claim 9, characterized in that 2,4-tolylene diisocyanate and 2,6-T oluylendiisocyanat be used as a mixture of at least one batch, preferably two mutually different batches, wherein the first batch of 2,4-tolylene diisocyanate to 2, Contains 6-tolylene diisocyanate in the ratio of 80 wt .-% to 20 wt .-% and the second batch of 2,4-tolylene diisocyanate to 2,6-T oluylendiisocyanat in the ratio of 67 wt .-% to 33 wt .-%, wherein the proportion of the second batch is at most 25 wt .-%, based on the total weight of the first and the second batch.

11. Flexible polyurethane foams, obtainable by a process according to one of claims 1 to 10. 12. Flexible polyurethane foams according to claim 11, characterized in that they are open-cell flexible polyurethane foams.

13. Flexible polyurethane foams according to claim 11 or 12, characterized in that the flexible polyurethane foams have a density according to DIN EN ISO 845: 2009-10 of 45.5 to 60.0 kg / m ³ .

14. Use of the flexible polyurethane foams according to one of claims 11 to 13 for the production of furniture upholstery, T extileinlagen, mattresses, automobile seats, headrests, armrests, sponges, foamed films for use in automotive parts such as headliners, door panels, seat covers and components.

15. Two-component system for the production of flexible polyurethane foams containing

a first component K1 comprising or consisting of:

Component A) comprising polyether carbonate polyol (component Al) and optionally one or more polyether polyols (component A2), the polyether polyols A2 being free of carbonate units,

B) if necessary

Bl) catalysts, and / or

B2) auxiliaries and additives

C) water and / or physical blowing agents, and

E) a compound having the following formula (I):

in which

R ^{1 is} an aromatic hydrocarbon radical having at least 5 carbon atoms or is a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical having at least 2 carbon atoms;

n is 1 to 3

and a second component K2 comprising or consisting of: D) diisocyanates and / or polyisocyanates which contain or consist of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate,