EP3768746A1

EP3768746A1 - Method for producing polyurethane soft foams with high bulk density

Info

Publication number: EP3768746A1
Application number: EP19711137.0A
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: 2019-03-21
Publication date: 2021-01-27
Also published as: WO2019180156A1; CN111954689A; US20210002412A1

Abstract

The invention relates to a method for producing polyurethane soft foams having a volumetric weight according to DIN EN ISO 845: 2009-10 from 50.0 to 80.0 kg/m³, in particular open-cell polyurethane soft foams based on polyether polyol and toluylene diisocyanate, having a high bulk density, wherein the resulting polyurethane foams have similar properties to the already known polyurethane soft foams, these being simpler and more sustainable in terms of their production.

Description

Process for the production of flexible polyurethane foams with high bulk density

The present invention relates to a process for the production of flexible polyurethane foams having a density according to DIN EN ISO 845: 2009-10 of 50.0 to 80.0 kg / m ³ , in particular of high density open-cell polyurethane foams based on polyetherpolyol and tolylene diisocyanate, the resulting polyurethane foams have similar properties to the previously known flexible polyurethane foams but are simpler and more sustainable in their manufacture.

In order to obtain flexible foams based on polyether polyol and toluylene diisocyanate with a desired open-cell content, two different batches of tolylene diisocyanate mixtures have hitherto been used. The first batch is a mixture of 80% by weight of 2,4-tolylene diisocyanate and 20% by weight of 2,6-tolylene diisocyanate obtainable by simple preparation, namely nitration and then reduction to amine and phosgenation. The second mixture consists of 67% by weight of 2,4-tolylene diisocyanate and 33% by weight of 2,6-tolylene diisocyanate and, in order to obtain the higher content of 2,6-tolylene diisocyanate, it must be worked up in a cost-intensive and labor-intensive manner. In this case, tolylene diisocyanate is crystallized out of the mixture in order to increase the proportion of 2,6-toluene diisocyanate. 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.

The object of the present invention was therefore to find a system for the production of flexible foams of high bulk density, in which the use of the reclaimed by crystallization charge of Toluylendiisocyanatgemischs 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.

The object of the present invention is achieved by a process for producing polyurethane foams having a density according to DIN EN ISO 845: 2009-10 of 50.0 to 80.0 kg / m ³ by reacting

Component A) containing one or more polyether polyols Al,

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,

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 is a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical having 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 in the present invention it is stated that a particular compound or radical may be substituted, then substituents known to the person skilled in the art are used. Particular preference is given to using one or more hydrogen atoms in the compounds by -F, -CI, -Br, -I , -OH, = O, -OR ³ , -OC (= O) R ³ , -C (= O) -R ³ , -NH ₂ , -NHR ³ , -NR ³ _{2 are} replaced, 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. 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 with 3 to 10 carbon atoms. In particular, the present invention relates to:

1. A process for the preparation of polyurethane foams having a density according to D1N EN 1SO 845: 2009-10 of 50.0 to 80.0 kg / m ³ , by reacting component A) containing one or more polyether polyols Al, in particular having a hydroxyl number according to D1N 53240-1: 2013-06 from 20 mg KOH / g to 250 mg KOH / g, preferably 40 to 60 mg KOH / g, and an ethylene oxide content 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 wt .-%, preferably 70 to 99 wt. %, more preferably 85 to 95% by weight (component Al), the polyether polyols Al preferably being free of carbonate units,

B) if necessary

Bl) catalysts, and / or

B2) auxiliaries and additives

C) water and / or physical blowing agents,

With

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

Contain or consist of tolylene diisocyanate;

the preparation being carried out at a ratio of 90 to 120, preferably 100 to 115, particularly preferably 102 to 110,

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;

R ^{2 is} a linear, branched, substituted or unsubstituted aliphatic

Hydrocarbon radical is; and

n is 1 to 3. Process according to aspect 1, characterized in that in formula (1)

R ^{1 is} an aromatic hydrocarbon radical having at least 6 carbon atoms or a linear, branched, substituted or unsubstituted aliphatic radical

Hydrocarbon 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; preferably R ^{1 is} an aromatic hydrocarbon 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 C4-12, more preferably C6-10, dicarboxylic acid esterified with a linear or branched C3-16 alkyl alcohol, in particular selected from bis (2-ethylhexyl) adipate and diisodecyl sebacate; or an ester of optionally substituted C5-16, more preferably CÖ-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 C _{6 -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 wt., Preferably 70 to 98 parts by wt., More preferably 90 to 95 wt. Parts, of one or more polyether polyols having a hydroxyl number according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 250 mg KOH / g, preferably 40 to 60 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 of 40 to 99.9% by weight, preferably 70 to 99% by weight, more preferably 85 to 95% by weight, the polyether polyols Al preferably being free of carbonate units,

A2 0 to 60 parts by wt., Preferably 0.1 to 20 wt. Parts 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,

A3 is from 0 to 60 parts by weight, preferably from 0.1 to 20 parts by weight, based on the sum of the parts by weight of components A1 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 in particular 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.

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

5. The method according to any one of the preceding aspects, characterized in that as component B

B 1 catalysts such

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.

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

Al 65 to 95 parts by weight of one or more polyether polyols having a hydroxyl value according to DIN 53240 of 20 mg KOH / g to 250 mg KOH / g, preferably 40 to 60 mg KOH / g, and a content of ethylene oxide of 0.10 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 70 to 99 wt. %, more preferably 85 to 95% by weight, wherein the polyether polyols are free from carbonate units, and

A2 5 to 35 parts by weight of one or more polyether carbonate polyols having a hydroxyl value according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 120 mg KOH / g or A3 5 to parts by weight of one or more polyether polyols having a hydroxyl number 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 .-%.

7. Process according to any one of the preceding aspects, characterized in that component A2 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 C0 ₂ - Has content of 15 to 25 wt .-%.

8. The method according to any one of the preceding aspects, characterized in that component D comprises at least 50 wt .-%, preferably at least 80 wt .-% 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.

9. Process according to one of the preceding aspects, characterized in that in component D at most 26.5% by weight of 2,6-tolylene diisocyanate are present, based on the total weight of component D, preferably wherein 22.0 to 26, 5 wt% of 2,6-tolylene diisocyanate based on the total weight of component D, more preferably wherein 20.0 to 23.3 wt% of 2,6-tolylene diisocyanate are contained based on the total weight of the component Component D, most preferably wherein 20.0% by weight of 2,6-tolylene diisocyanate are included, based on the total weight of component D.

10. The process according to aspect 9, characterized in that 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate are used as a mixture of at least one batch, preferably two mutually different batches, wherein the first batch of 2,4-tolylene diisocyanate to 2.6 Toluene diisocyanate in the ratio of 80 wt .-% to 20 wt .-% and the second batch of 2,4-tolylene diisocyanate to 2,6-tolylene diisocyanate in the ratio of 67 wt .-% to 33 wt .-%, wherein the Amount of the second charge is at most 25 wt .-%, preferably at most 10 wt .-%, based on the total weight of the first and the second batch, more preferably wherein only the two batches are used as component D. 11. Polyurethane foams having a density according to DIN EN ISO 845: 2009-10 of 50.0 to 80.0 kg / m ³ , obtainable by a process according to any one of aspects 1 to 10.

12. polyurethane foams according to aspect 11, characterized in that it is polyurethane flexible foams, in particular open-cell polyurethane flexible foams.

13. Polyurethane foams according to aspect 11 or 12, characterized in that the polyurethane foams have a density according to DIN EN ISO 845: 2009-10 of 65.0 to 75.0 kg / m ³ .

14. Use of the polyurethane foams according to any one of aspects 11 to 13 for the manufacture of furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges, foam sheets for use in automotive parts such as headliners, door panels, seat cushions and building components.

15. Two-component system for the production of polyurethane foams having a density according to DIN EN ISO 845: 2009-10 of 50.0 to 80.0 kg / m ³ comprising a first component K ¹ comprising or consisting of:

Component A) comprising one or more polyether polyols, in particular having a hydroxyl number according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 250 mg KOH / g, preferably 40 to 60 mg KOH / g, and a content of ethylene oxide of 0.10 to 59.0 wt .-% (component Al), wherein the polyether polyols Al are preferably 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 tolylene 2,6-diisocyanate,

and at least one catalyst, wherein the component Kl and the component K2 in a ratio of an isocyanate index of 90 to 120, preferably 100 to 115, more preferably 102 to 110, 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 the production of polyurethane foams, preferably flexible polyurethane foams, by reacting

Al> 40 to <100 parts by weight, preferably> 60 to <100 parts by weight, more preferably> 80 to <100 parts by weight of one or more polyether polyols having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <250 mg KOH / g, preferably 40 to 60 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 of 40 to 99.9 wt .-%, preferably 70 to 99 wt .-%, more preferably 85 to 95 wt -.%, Wherein the polyether polyols are in particular free of carbonate units Al

A2 <60 to> 0 parts by wt., Preferably <40 to> 0.1 wt. Parts, particularly preferably <20 to> 1 wt. Parts, 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,

A3 <60 to> 0 parts by weight, preferably 0.1 to 20 parts by weight, based on the sum of the parts by weight of the components Al and A2, 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 in particular free of carbonate units, A4 <40 to> 0 parts by weight, preferably 0.1 to 20 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 0.1 to 20 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 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,

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 <95 to> 65 parts by wt., Most preferably <90 to> 85 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, preferably 40 to 60 mg KOH / g, and an ethylene oxide content 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 of From 40 to 99.9% by weight, preferably from 70 to 99% by weight, more preferably from 85 to 95% by weight, the polyether polyols Al being in particular free from carbonate units, and

A2> 5 to <35 parts by wt., Most preferably> 10 to <15 wt. Parts of one or more Polyethercarbonatpolyole having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to <120 mg KOH / g and preferably a C0 ₂ content of 15 to 25% by weight,

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

In another embodiment, component A comprises Al <95 to> 65 parts by wt., Preferably <90 to> 80 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, preferably 40 to 60 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 of 40 up to 99.9% by weight, preferably 70 to 99% by weight, more preferably 85 to 95% by weight, the polyether polyols Al preferably being free of carbonate units, and A2> 3 to <33 parts by weight, preferably> 8 to <18 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 and preferably a C0 ₂ content of 15 to 25 wt .-%,

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 in particular free of carbonate units,

component A is preferably free of component A4. In a further embodiment component A comprises

Al <99 to> 60 parts by wt., Preferably <95 to> 75 wt. Parts, particularly preferably <90 to> 85 wt. Parts, most preferably <35 to> 25 wt. Parts of one or more polyether polyols a hydroxyl number according to D1N 53240 of> 20 mg KOH / g to <250 mg KOH / g and an ethylene oxide content 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 wt .-%, preferably 70 to 99 wt .-%, more preferably 85 to 95 wt -.%, Wherein the polyether polyols Al preferably free of carbonate are and

A2> 0.05 to <39.9 parts by wt., Preferably> 4.99 to <24.99 wt. Parts, particularly preferably> 9.99 to <14.99 wt. Parts, 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 and preferably a C0 ₂ content of 15 to 25 wt .-%,

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 PlPA 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, polyols which are not covered by the definition of the components Al to A4 fall, wherein the component A is preferably free from Component A3. The specified ranges and preferred ranges of the components A1, A2, A4 and A5 are freely combinable with one another.

Particularly preferably, component A consists only of Al.

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

Component Al

The component Al 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. In preferred aspects, the component Al is free of carbonate moieties.

The preparation of the compounds according to Al 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-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1- pentenoxide, 2,3-pentenoxide, 2-methyl-l, 2-butene oxide, 3-methyl-1,2-butene oxide, l-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl- l, 2-pentenoxide, 4-methyl-l, 2-pentenoxide, 2-ethyl-1, 2-butene oxide, 1-epoxide, 1-octene oxide, 1-nonoxide, 1-decene oxide, 1-undecenoxide, 1-dodecene oxide, 4-methyl-l, 2-pentenoxide, butadiene monoxide, isoprene monoxide, cyclopentene oxide, cyclohexene oxide, cycloheptenoxide, cyclooctene oxide, styrene oxide, methylstyrene oxide, pinene oxide, mono- or poly-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 glycidyls ether, glycidyl methacrylate and also epoxy-functional alkyoxysilanes, for example 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3-glycidyloxypropylmethyl-dimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, 3

Glycidyloxypropyltrlisopropoxysilan. The alkylene oxides used are preferably ethylene oxide and / or propylene oxide and / or 1,2-butylene oxide. Particularly preferred is a Excess of propylene oxide and / or 1, 2-butylene oxide used. The alkylene oxides can be fed 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, l, 3-butanediol, 1, 4-butanediol, hexanediol, pentanediol, 3-methyl-l, 5-pentanediol, l, l2-dodecanediol , Glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, pyrocatechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, condensates of formaldehyde and phenol or melamine or urea containing methylol groups. These can also be used in mixture. The starter compound used is preferably 1,2-propylene glycol and / or glycerol and / or trimethylolpropane and / or sorbitol.

The polyether polyols according to Al 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 A2

Component A2 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 KOH / g, more preferably from> 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, wherein the polyethercarbonate polyol is preferably has a CO2 content of 15 to 25 wt .-%. Component A2 preferably 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 several H-functional starter molecules having an average functionality of> 1 to <6, preferably from> 1 to <4, especially preferably from> 2 to <3. In the context of the invention, "H-functional" is understood to mean a starter compound which has active H atoms in relation to alkoxylation.

The copolymerization of carbon dioxide and one or more alkylene oxides is preferably carried out 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 (11) is merely to be understood so 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 (11) 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 ("carbon dioxide-derived units", "CCk content") in a polyethercarbonate polyol can be determined from the evaluation of characteristic signals in the H-NMR spectrum. The following example illustrates the determination of the level of carbon dioxide-derived moieties in a C0 ₂ / propylene oxide polyether carbonate polyol started on l, 8-octanediol.

The proportion of incorporated CO.sub.2 in a polyethercarbonate polyol and the ratio of propylene carbonate to polyethercarbonate polyol can be determined by 1H-NMR (a suitable device is from Broker, DPX 400, 400 MHz, pulse program zg30, waiting time dl: 10s, 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 (ie, with no incorporated carbon dioxide) with 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),

_{£ e} . F (5.1 - 4. ₈ ) - _f (4.5)] - 102 _{tl 0 (>} , _{/ o}

N (HI)

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, 1-4,8) = 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-l, 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),

where the value for 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 CCk-free conditions, and polyether carbonate polyol, composed of starter, propylene oxide and carbon dioxide during the in the presence of CO2 activation steps and during copolymerization), the non-polymer constituents of the reaction mixture (ie, cyclic propylene carbonate and any unreacted propylene oxide present) have been computationally eliminated. 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 indication of the C0 ₂ 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 polyethercarbonate polyol molecule present from the initiator (1, US Pat. 8-octanediol, if any) and from the reaction of the initiator with epoxide resulting added under C0 ₂ -free conditions was not considered).

For example, the preparation of polyethercarbonate polyols according to A2 comprises:

(A) an H-functional initiator compound or a mixture of at least two H-functional starter compounds and optionally water and / or other volatile compounds by increased 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 CO2 can be carried out, and in which case the temperature peak occurring due to the following exothermic chemical reaction ("hotspot") and / or a pressure drop in the reactor is respectively awaited, and wherein the step (β) for activating can also take place several 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, alkylene oxides (epoxides) having 2 to 24 carbon atoms can be used to prepare the polyethercarbonate polyols A2. 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-pentoxide, 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- l, 2-pentenoxide, 4-methyl-l, 2-pentenoxide, 2-ethyl-l, 2-butene oxide, 1-epoxide, 1-octene oxide, 1-nonoxide, 1-decene oxide, 1-undecenoxide, 1-dodecenoxide, 4-methyl-1, 2-pentene oxide, butadiene monoxide, isoprene monoxide, cyclopentene oxide, cyclohexene oxide, cycloheptenoxide, cyclooctene oxide, styrene oxide, methylstyrene oxide, pinene oxide, mono- or poly-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 glycine butyl ether, glycidyl methacrylate, and epoxy functional alkoxysilanes such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, 3-glycidyloxypropyltriisopropoxysilane. Preferably, the alkylene oxides used are 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 starter compound compounds with 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, amino alcohols, thio alcohols, hydroxy esters, polyether polyols, polyester polyols, polyester ether, polyether carbonate, polycarbonate, polycarbonates, polyethyleneimines Polyetheramines (eg so-called Jeffamine® from Huntsman, such as eg D-230, D-400, D-2000, T-403, T-3000, T-5000 or corresponding products of BASF, such as e.g. Polyetheramine D230, D400, D200, T403, T5000), polytetrahydrofurans (eg, BASF's PolyTHF®, such as PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800, 2000), Polytetrahydrofuranamine (BASF product polytetrahydrofuran amine 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 fatty acid esters, which in Agent containing at least 2 OH groups per molecule used. By way of example, the C1-C24 alkyl fatty acid esters which contain on average at least 2 OH 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, lt-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.

As H-functional starter compounds suitable polyhydric alcohols are, for example, dihydric alcohols (such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, l, 3-propanediol, 1, 4-butanediol, 1, 4-butenediol, 1, 4-butynediol, neopentyl glycol, l , 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), and 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, Desmophen® 50RE40). 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. Succinic, maleic, maleic, adipic, phthalic, phthalic, isophthalic, terephthalic, tetrahydrophthalic,

Tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of said acids and / or anhydrides used. As alcohol components z. B. ethanediol, 1, 2-propanediol, l, 3-propanediol, 1, 4-butanediol, l, 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 used. 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 prepared beforehand in a separate reaction step for this purpose.

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

HO- (CH ₂ ) _x -OH (VI) where x is a number from 1 to 20, preferably an even number from 2 to 20. Examples of alcohols according to formula (VI) 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, and 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, 1,1-pentanediol, 2-methylpropane-1, 3-diol, neopentyl glycol, l, 6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, wherein the polyether polyol from 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 A2 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.

DMC catalysts are known, in principle, 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, e.g. 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 00/47649 a very high activity in the homopolymerization of epoxides and allow the preparation of polyether polyols and / or polyether carbonate polyols at very low catalyst concentrations (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 A2 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 A2 have a hydroxyl number of> 20 mg KOH / g to <250 mg KOH / g and are obtainable by copolymerization from> 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 polyethercarbonate polyol A2 is used, comprising blocks of the formula (II) where the ratio e / f is from 2: 1 to 1:20.

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

As alkylene oxides and H-functional starter compounds are the same in question, as described for component Al.

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 arise. 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 trifunctional 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 which contain portions of free radical polymerization monomers such as styrene or acrylonitrile in a base polyol, e.g. a polyether polyol and / or Polyethercabonatpolyol, produced solid polymers.

PHD (polyurea dispersion) polyols are prepared, for example, by in situ polymerization 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-tolylene 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 trifunctional initiator (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, wherein the polyether (carbonate) polyol has a functionality of 2.5 to 4 and a hydroxyl number of> 3 mg KOH / g to <112 mg KOH / g (molecular weight 500 to 18,000). 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 may be, for example, low molecular weight diols (eg 1, 2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (eg glycerol, trimethylolpropane) and tetraoie (eg 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 can e.g. Also be used ethylenediamine and triethanolamine started polyethers. These compounds are not among the compounds according to the definition of component B2.

Component B

As catalysts according to the component B 1 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), stannous (II ) Salt of 2-butyloctanoic acid, stannous salt of 2-hexyldecanoic acid, stannous salt of neodecanoic acid, stannous salt of isononanoic acid, tin (II) salt of oleic acid, stannous (II ) Salt of ricinoleic acid and tin (II) laurate used. In a preferred embodiment of the invention, at least one tin (II) salt of the formula (VII) Sn (CxH _{2x + i} COO) ₂ (VII) used, where 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) ricinoleate and stannous salt of 2-hexyl decanoic acid, i. Tin (II) - (2-hexyldecanoate) used.

In another preferred embodiment of the invention is as component Bl 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 a maximum of 50 wt .-% based on component Bl may be used.

Component Bl.l comprises urea and derivatives of urea. As derivatives of urea, mention may be made, for example, of aminoalkyl ureas, e.g. (3-Dimethylaminopropylamine) - urea and l, 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> 0.05 to <1.5 parts by weight, preferably from> 0.1 to <0.5 parts by weight, particularly preferably from> 0.25 to <0, 35 parts by weight, based on the sum of the parts by weight of 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 from> 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 the components Al to A2 used.

The content of amine catalysts in component Bl.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 Bl.2 is free from amine catalysts. As catalysts of component Bl.2, for example, the tin (II) salts of carboxylic acids described above can be used.

As minor amounts (see above), if appropriate, aminic catalysts may be mentioned: aliphatic tertiary amines (for example trimethylamine, tetramethylbutanediamine, 3-dimethylaminopropylamine, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine), cycloaliphatic tertiary amines (for example 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 aminoethers (e.g., 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 according to 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 whiting) 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 be used according to the invention and details of the use and mode of action of these auxiliaries and additives are published 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-tolylene diisocyanate and 2,6-tolylene 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 2,4- and 2,6-toluene diisocyanate, and any desired mixtures of these with isomers ("TDI") are preferred; Polyphenylpolymethylenpolyisocyanate as prepared by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret polyisocyanates ("modified polyisocyanates"), especially those modified polyisocyanates, which differs from Derive 2,4- and / or 2,6-toluene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethane diisocyanate. 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 polyphenylpolymethylene polyisocyanate ("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% of 2,4-tolylene diisocyanate.

According to the invention, the characteristic number in the process according to the invention is> 90 to <120. The code is preferably in a range of> 100 to <115, more preferably> 102 to <110. The index (index) indicates the percentage ratio of the isocyanate actually used. Amount to stoichiometric, ie for the implementation of OH equivalents calculated amount of isocyanate groups (NCO) amount.

Ratio = (isocyanate amount used): (calculated amount of isocyanate) · 100 (VIII)

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 or A3 in 0 to 30 wt .-%, in particular 10 wt .-% or 0 wt .-%, wherein the sum of the components Al and A2 or A3 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% by weight of Al; 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 or

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

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

To prepare the polyurethane foams, the reaction components are preferably reacted according to the conventional one-step process, often using machinery, e.g. those described in EP-A 355 000. Details of processing equipment which may also be used according to the invention are given in the Plastics Handbook, Volume VII, by Vieweg and

Höchtlen, Carl-Hanser-Verlag, Munich 1993, e.g. on pages 139 to 265.

The polyurethane foams are preferably in the form of flexible polyurethane foams and can be produced as molded or also as slab foams, preferably as slab foams. The invention therefore relates to a process for the preparation of the polyurethane foams, the polyurethane foams produced by these processes, the polyurethane foam foams produced by these processes or

Flexible polyurethane foams, the use of flexible polyurethane foams for the production of molded parts and the molded parts themselves.

The polyurethane foams obtainable according to the invention preferably

Flexible polyurethane foams, for example, find the following application:

Furniture upholstery, textile liners, mattresses, automobile seats, headrests, armrests, sponges, foam sheets for use in automotive parts such as headliners, door paneling, seat pads and building components. Examples

Component A:

Al-1 ARCOL POLYOL 1108: propylene oxide / ethylene oxide based polyol; prepared by DMC catalysis; Starter: glycerin; OH number: 48 mg KOH / g

Component B:

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

Bl 2-l, 4-diazabicyclo [2.2.2] octane (33 wt .-%) in dipropylene glycol (67 wt .-%) (Dabco 33 LV ^®, Evonik, Essen, Germany).

Bl -3 tin (II) 2-ethylhexanoate (Dabco T-9, commercially available from Evonik, Essen, Germany)

B2-1 polyether-based foam stabilizer Tegostab ^® B 8002 (Evonik, Essen, Germany)

B2-2 polyether-based foam stabilizer Tegostab ^® B 8244 (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 from 48 to 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 E-4: acetyltributyl citrate commercially available as Citrofol BII

E-5: tris (2-ethylhexyl) trimellitate also called trioctylmellitate

E-6: trioctyldodecyl citrate, commercially available as Siltech CE-2000 from Siltech

Corporation

E-7: hexylhexanoate

Production of polyurethane foams

Under the processing conditions customary for the production of 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 according to DIN EN ISO 845: 2009-10

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 examples according to the invention are given as Ex.

Table 1: VBsp 1 and Ex. 1 to 5, continuation of the table on the next page Ex. 6 to 10; pphp = parts per 100 parts polyol;

Claims

Claims:

1. A process for producing polyurethane foams having a density according to DIN EN ISO 845: 2009-10 of 50.0 to 80.0 kg / m ³ by reacting component A) comprising one or more polyether polyols Al (component Al),

B) if necessary

Bl) catalysts, and / or

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 tolylene diisocyanate;

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

in which

R ^{2 is} a linear, branched, substituted or unsubstituted aliphatic

Hydrocarbon radical is; and

n is 1 to 3.

2. The method according to claim 1, characterized in that in formula (I)

Hydrocarbon radical having 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.

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

Al 40 to 100 parts by wt. 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 from 0.10 to 59.0 wt .-%;

A2 0 to 60 parts by weight of one or more polyethercarbonate polyols having a hydroxyl number according to DIN 53240-1: 20l3-06 of 20 mg KOH / g to 120 mg KOH / g,

A3 0 to 60 parts by wt., Based on the sum of the parts by wt. Of the components Al and A2, 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 .-%,

A4 0 to 40 parts by wt., Based on the sum of the parts by wt. Of the components Al and A2, one or more polymer polyols, PHD polyols and / or PIPA polyols, A5 0 to 40 parts by wt., 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 A1 to A4, wherein all parts by weight of the components Al, A2, A3, A4, A5 are normalized such that Al + A2 in of the composition 100.

4. The method according to any 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 wt., Wherein all parts by weight of the compound E relate to 100 parts by weight of the components Al ,

5. The method according to any one of the preceding claims, characterized in that as component B

Bl catalysts like

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 75 to 100 parts by weight of one or more polyether polyols with a

Hydroxyl number according to DIN 53240 from 20 mg KOH / g to 250 mg KOH / g and a content of ethylene oxide from 0.10 to 59.0 wt .-%, wherein Al is free of carbonate units; and

A2 0 to 25 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 or A3 0 to 25 parts by weight of one or more polyether polyols one

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 .-%.

7. The method according to any one of the preceding claims, characterized in that component A2 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-tolylene diisocyanate and 2,6-tolylene diisocyanate.

9. The method according to any one of the preceding claims, characterized in that in component D at most 26.5 wt .-% of 2,6-toluene diisocyanate are present, 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-tolylene diisocyanate are used as a mixture of at least one batch, preferably two mutually different batches, wherein the first batch of 2,4-tolylene diisocyanate to 2.6 Toluene diisocyanate in the ratio of 80 wt .-% to 20 wt .-% and the second batch of 2,4-tolylene diisocyanate to 2,6-tolylene diisocyanate in the ratio of 67 wt .-% to 33 wt .-%, wherein the Proportion of the second batch is at most 50 wt .-%, based on the total weight of the first and the second batch.

11. The method according to any one of the preceding claims, characterized in that the preparation is carried out at a ratio of 100 to 115, in particular at 102 to 110th

12. Polyurethane foams having a density according to DIN EN ISO 845: 2009-10 of 50.0 to 80.0 kg / m ³ , in particular from 65.0 to 75.0 kg / m ³ , obtainable by a process according to one of the claims 1 to 11.

13. polyurethane foams according to claim 12, characterized in that it is flexible polyurethane foams, in particular open-cell polyurethane flexible foams.

14. The use of the polyurethane foams according to any one of claims 12 and 13 for the production of furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges, foamed films for use in automotive parts such as headliners, door side panels, seat covers and components.

Component A) containing one or more polyether polyols Al (component Al),

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

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,

and at least one catalyst, wherein the component Kl and the component K2 are in a ratio of an isocyanate index of 90 to 120 to each other.