Method for producing polyether carbonate polyols

Abstract

The invention relates to a method for producing polyether carbonate polyols, (i) one or more alkylene oxide(s) and carbon dioxide being added to one or more H-functional starter substance(s) in the presence of a double metal cyanide catalyst or in the presence of a metal complex catalyst based on the metals zinc and/or cobalt, a reaction mixture containing the polyether carbonate polyol being obtained, characterized in that (ii) at least one component K is added to the obtained reaction mixture containing the polyether carbonate polyol, wherein component K is selected from at least one compound that contains a phosphorus-oxygen bond or a compound of phosphorus that can form one or more P—O bonds by reaction with OH-functional compounds.

Claims

1. A process for preparing polyether carbonate polyols, comprising (i) adding one or more alkylene oxide(s) and carbon dioxide onto one or more H-functional starter substance(s) in the presence of a double metal cyanide catalyst to obtain a reaction mixture comprising the polyether carbonate polyol, and (ii) adding at least one component K to the reaction mixture comprising the polyether carbonate polyol obtained in (i), wherein component K is at least one compound containing a phosphorus-oxygen bond or a compound of phosphorus that can form one or more P—O bonds by reaction with one or more OH-functional compounds.

2. The process of claim 1, wherein the content of volatile constituents in the polyether carbonate polyol from step (i) is reduced by thermal means at a temperature of 80° C. to 200° C. prior to step (ii).

3. The process of claim 1, wherein (iii) the content of volatile constituents in the reaction mixture from step (ii) is reduced by thermal means at a temperature of 80° C. to 200° C.

4. The process of claim 3, comprising (iv) adding at least one component K to the reaction mixture comprising the polyether carbonate polyol from step (iii).

5. The process of claim 4, wherein in step (iv) component K is added in an amount of from 20 ppm to 1000 ppm.

6. The process of claim 1, wherein in step (ii) component K is added in an amount of from 20 ppm to 1000 ppm.

7. The process of claim 1, wherein component K is selected from at least one compound from the group consisting of phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, phosphonous acid, phosphinous acid, phosphine oxides and salts, esters, halides and amides of phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, phosphonous acid, phosphinous acid, phosphorus(V) sulfide, phosphorus tribromide, phosphorus trichloride and phosphorus triiodide.

8. The process of claim 1, wherein component K is selected from at least one compound selected from the group consisting of phosphoric acid, mono-, di- or trialkyl esters of phosphoric acid, mono-, di- or triaryl esters of phosphoric acid, mono-, di- or trialkaryl esters of phosphoric acid, (NH.sub.4).sub.2HPO.sub.4, phosphonic acid, mono- or dialkyl esters of phosphonic acid, mono- or diaryl esters of phosphonic acid, mono- or dialkaryl esters of phosphonic acid, phosphorous acid, mono-, di- or trialkyl esters of phosphorous acid, mono-, di- or triaryl esters of phosphorous acid, mono-, di- or trialkaryl esters of phosphorous acid, phosphinic acid, phosphonous acid and phosphinous acid.

9. The process of claim 1, wherein component K is at least one compound selected from the group consisting of phosphoric acid, dibutyl phosphate, triethyl phosphate, phosphonic acid and (NH.sub.4).sub.2HPO.sub.4.

10. The process of claim 1, wherein the polyether carbonate polyol corresponds to formula (Ia) ##STR00004## wherein the ratio of e:f is from 2:1 to 1:20.

Description

EXAMPLES

Methods

(1) OH Number:

(2) The OH numbers (hydroxyl numbers) were determined in accordance with DIN 53240.

(3) Viscosity:

(4) Viscosities were determined by rotational viscometer (Anton Paar Physica MCR 51) at a shear rate of 5 s.sup.−1 in accordance with DIN 53018.

(5) GPC:

(6) The number-average molecular weight M.sub.n and the weight-average molecular weight M.sub.w, and also the polydispersity (M.sub.w/M.sub.n), of the products was determined by means of gel permeation chromatography (GPC). The procedure of DIN 55672-1 was followed: “Gel permeation chromatography, Part 1—Tetrahydrofuran as eluent” (SECurity GPC System from PSS Polymer Service, flow rate 1.0 ml/min; columns: 2×PSS SDV linear M, 8×300 mm, 5 μm; RID detector). Polystyrene samples of known molar mass were used for calibration.

(7) CO.sub.2 Content in the Polyether Carbonate Polyol:

(8) The fraction of incorporated CO.sub.2 in the resulting polyether carbonate polyol and the ratio of propylene carbonate to polyether carbonate polyol were determined by .sup.1H-NMR (Bruker DPX 400, 400 MHz; pulse programme zg30, d1 relaxation delay: 10 s, 64 scans). Each sample was dissolved in deuterated chloroform. The relevant resonances in the .sup.1H-NMR (based on TMS=0 ppm) are as follows:

(9) Cyclic carbonate (which was formed as a by-product) having a resonance at 4.5 ppm, carbonate resulting from carbon dioxide incorporated in the polyether carbonate polyol having resonances at 5.1 to 4.8 ppm, unreacted PO having a resonance at 2.4 ppm, polyether polyol (i.e. without incorporated carbon dioxide) having resonances at 1.2 to 1.0 ppm, the 1,8-octanediol incorporated as starter molecule (if present) having a resonance at 1.6 to 1.52 ppm.

(10) The mole fraction of the carbonate incorporated in the polymer in the reaction mixture is calculated as per formula (VIII) as follows, the following abbreviations being used:

(11) A(4.5)=area of the resonance at 4.5 ppm for cyclic carbonate (corresponds to a hydrogen atom)

(12) A(5.1-4.8)=area of the resonance at 5.1-4.8 ppm for polyether carbonate polyol and a hydrogen atom for cyclic carbonate

(13) A(2.4)=area of the resonance at 2.4 ppm for free, unreacted PO

(14) A(1.2-1.0)=area of the resonance at 1.2-1.0 ppm for polyether polyol

(15) A(1.6-1.52)=area of the resonance at 1.6 to 1.52 ppm for 1,8-octanediol (starter), if present.

(16) Taking into account the relative intensities the values for the polymer-bound carbonate (“linear carbonate” LC) in the reaction mixture were converted into mol % as per the following formula (VIII).

(17) $\begin{array}{cc}\mathrm{LC}=\frac{A\left(5,1-4,8\right)-A\left(4,5\right)}{\begin{array}{c}A\left(5,1-4,8\right)+A\left(2,4\right)+0,33*\\ A\left(1,2-1,0\right)+0,25*A\left(1,6-1,52\right)\end{array}}*100& \left(\mathrm{VIII}\right)\end{array}$

(18) The weight fraction (in % by weight) of polymer-bound carbonate (LC′) in the reaction mixture was calculated as per formula (IX),

(19) $\begin{array}{cc}{\mathrm{LC}}^{\prime }=\frac{\left[A\left(5,1-4,8\right)-A\left(4,5\right)\right]*102}{D}*100\%& \left(\mathrm{IX}\right)\end{array}$
where the value of D (“denominator” D) is calculated as per formula (X):
D=[A(5,1−4,8)−A(4,5)]*102+A(4,5)*102+A(2,4)*58+0,33*A(1,2-1,0)*58+0,25*A(1,6−1,52)*146  (X)

(20) The factor 102 results from the sum of the molar masses of CO.sub.2 (molar mass 44 g/mol) and of propylene oxide (molar mass 58 g/mol), the factor of 58 results from the molar mass of propylene oxide and the factor of 146 results from the molar mass of the 1,8-octandediol starter used (if present).

(21) The weight fraction (in % by weight) of cyclic carbonate (CC′) in the reaction mixture was calculated as per formula (XI):

(22) $\begin{array}{cc}{\mathrm{CC}}^{\prime }=\frac{A\left(4,5\right)*102}{D}*100\%& \left(\mathrm{XI}\right)\end{array}$
where the value of D is calculated as per formula (X).

(23) In order to calculate the composition based on the polymer fraction (consisting of polyether polyol which has been formed from starter and propylene oxide during the activation steps which take place under CO.sub.2-free conditions, and polyether carbonate polyol formed from starter; propylene oxide and carbon dioxide during the activation steps which take place in the presence of CO.sub.2 and during the copolymerization) from the values for the composition of the reaction mixture, the non-polymeric constituents of the reaction mixture (i.e. cyclic propylene carbonate and any unconverted propylene oxide present) were mathematically eliminated. The weight fraction of the repeat carbonate units in the polyether carbonate polyol was converted to a weight fraction of carbon dioxide using the factor F=44/(44+58). The value for the CO.sub.2 content in the polyether carbonate polyol is normalized to the fraction of the polyether carbonate polyol molecule formed in the copolymerization and any activation steps in the presence of CO.sub.2 (i.e. the fraction of the polyether carbonate polyol molecule resulting from the starter (octane-1,8-diol, if present) and from the reaction of the starter with epoxide added under CO.sub.2-free conditions was not taken into account here). In each case the CO.sub.2-content, the hydroxyl number and the employed starter were used to calculate the e/f ratio (see formula (Ia)) for the respective polyether carbonate polyol.

(24) DMD Content:

(25) The qualitative and quantitative determination of the dimethyldioxanes (DMD hereinbelow) from polyether carbonate polyols was performed by headspace GC/MS.

(26) Instruments employed:

(27) Gas chromatograph:

(28) Manufacturer: Thermo Scientific

(29) Model: Trace GC Ultra

(30) Serial number: 6201252621

(31) Mass spectrometer:

(32) Manufacturer: Thermo Scientific

(33) Model: ISQ Single Quadrupole MS

(34) Serial number: ISQ121046

(35) Headspace sampler:

(36) Manufacturer: Perkin Elmer

(37) Model: Turbo Matrix 40 Trap

(38) Serial number: M41L0505273

(39) 1. Method

(40) The samples were stored tightly sealed, in a refrigerator at 5° C. until immediately prior to weighing. About 10 to 15 mg of the particular sample were transferred into a volumetrically accurate 22 ml headspace sample vial and accurately weighed to ±0.3 mg (nominally ±0.1 mg). The sample vial was carefully sealed and brought to 150° C. for 15 minutes in the headspace inlet system (Perkin Elmer TurboMatrix 40 Trap Headspace Sampler). The injection needle was then introduced to achieve pressure buildup and the pressure was brought to 236 kPa over 2 minutes. The injection needle was finally introduced fully and sample was injected from the headspace into the transfer line 1 (between headspace sampler and gas chromatograph) for 0.08 minutes (4.8 sec). Needle temperature: 153° C.; temperature of the transfer line 1: 157° C.

(41) GC parameters: injector temperature 210° C., injector pressure 210 kPa, GC injector split 10 ml/min, additional split downstream of the GC injector onto two Restek Rxi-5Sil MS columns (dimethylsiloxane with 5% phenyl fraction), each having a length of about 20 m, an internal diameter of 0.15 mm and a film thickness of 2 μm. Temperature program: 2 min at 45° C., from 45° C. to 150° C. at 12° C./min, from 150° C. to 310° C. at 45° C./min, 15 min at 310° C. GC instrument:

(42) Thermo Trace GC Ultra.

(43) Detection column 1: FID, 280° C., hydrogen 37 ml/min, air 320 ml/min. Makeup gas helium 15 ml/min.

(44) Detection column 2: 70 eV EI-MS with Thermo ISQ, temperature of the transfer line 2 (between the end of column 2 and the MS ion source) 270° C., ion source temperature 250° C., mass range 20 to 420 Dalton (z=1), scan duration 0.4 sec.

(45) 2. Assignment

(46) Assignment was carried out based on the 70 eV EI mass spectra. Four isomers appear in the RT range 8 to 10 min. The spectra for these isomers are barely distinguishable: Molecular ion m/z 116, base peak m/z 42, logical neutral loss of 15 mass units to m/z 101 (M-CH3).

(47) 3. Quantitative Determination

(48) The quantitative determinations were based upon external calibration with a distillate comprising about 70% by weight of dimethyldioxanes. The absolute dimethyldioxane content in the distillate was determined by quantitative 1H-NMR (Q-NMR). External calibration was performed as a factor method with determination in duplicate. FID area counts were determined as sum values for 4 isomers. The absolute dimethyldioxane mass was determined using the factor and the concentration in the particular sample was determined via the exact sample weight. Determinations were generally carried out in duplicate. As a safeguard, the factor was frequently checked via repeat measurements.

(49) Chemicals:

(50) Each of the phosphorus additives employed in the examples (component K) was purchased from Sigma-Aldrich Chemie GmbH, Munich, Germany.

(51) Preparation of Polyether Carbonate Polyol a

(52) A nitrogen-purged 60 L pressure reactor comprising a gas metering means was initially charged with a suspension of 16.0 g of dried DMC catalyst (prepared as per example 6 of WO 01/80994 A1) and 4700 g of cyclic propylene carbonate (cPC). The reactor was heated to about 100° C. and inertized with N.sub.2 at reduced pressure (100 mbar) for 1 h. The reactor was then pressurized to 74 bar with CO.sub.2. 500 g of propylene oxide (PO) were rapidly metered into the reactor at 110° C. with stirring (316 rpm). The start of the reaction was signalled by a temperature spike (“hotspot”) and a pressure drop. After activation the reactor was simultaneously charged with the remaining propylene oxide (32.04 kg) at 8.7 kg/h and 1.188 kg of the starter glycerol (spiked with 180 ppm of 85% H.sub.3PO.sub.4) at 0.4 kg/h. The reaction temperature was simultaneously lowered to 105° C. The progress of the reaction was monitored via CO.sub.2 consumption while continuously controlled topping-up maintained the pressure in the reactor at the abovementioned value (74 bar). Once PO addition was complete the mixture was stirred at 316 rpm at 105° C. until no further reduction in pressure was observed. The resulting product was divided into two batches.

(53) Batch 1:

(54) For the first batch the thermal reduction in the content of volatile constituents was carried out using a thin film evaporator (T=140° C., p<3 mbar, 400 rpm). The resulting polyether carbonate polyol A1 was analyzed and the following results were obtained.

(55) Polyether Carbonate Polyol A1:

(56) OH number=55.8 mg KOH/g

(57) Viscosity (25° C.)=19650 mPas

(58) CO.sub.2 content=20.0%

(59) Polydispersity (M.sub.w/M.sub.n)=1.12

(60) DMD content=360 ppm

(61) e/f ratio=1/1.91

(62) Batch 2:

(63) For the second batch the thermal reduction in the content of volatile constituents was carried out by thin-filming twice over a thin film evaporator (T=140° C., p<3 mbar, 400 rpm). The resulting polyether carbonate polyol A2 was analyzed and the following results were obtained.

(64) Polyether Carbonate Polyol A2

(65) OH number=55.2 mg KOH/g

(66) Viscosity (25° C.)=17400 mPas

(67) CO.sub.2 content=20.0%

(68) Polydispersity (M.sub.w/M.sub.n)=1.12

(69) DMD content=140 ppm

(70) e/f ratio=1/1.92

(71) Storage Tests with Polyether Carbonate Polyol A1:

Comparative Example 1

(72) 100 g of the polyether carbonate polyol A1 were stored in a sealed screwtop vial for 24 h at 180° C. The DMD content of the stored polyether carbonate polyol A1 was then determined.

Examples 2 to 4

(73) 100 g of the employed polyether carbonate polyol A1 were mixed with the type and amount of component K reported in table 1 and stored in a sealed screwtop vial for 24 hours at 180° C. The DMD content of the stored polyether carbonate polyol was then determined in each case.

(74) TABLE-US-00001 TABLE 1 Storage tests with polyether carbonate polyol A1: Storage Storage DMD temperature time content Example Component K [° C.] [h] [ppm] 1 (comp.) — 180 24 3256 2 125 ppm of phosphoric acid 180 24 212 3 270 ppm of dibutyl 180 24 319 phosphate 4 500 ppm of triethyl 180 24 180 phosphate  4a 5000 ppm of triethyl 180 24 322 phosphate comp = comparative example

(75) The tests summarized in table 1 were carried out starting with polyether carbonate polyol A1 having a DMD content of 360 ppm. The results in table 1 show that the polyether carbonate polyol A1 comprising component K surprisingly has a lower DMD content after thermal storage (examples 2 to 4) and that the DMD content in the polyether carbonate polyol A1 markedly increases after thermal storage without component K (comparative example 1).

(76) Storage Tests with Polyether Carbonate Polyol A2:

Comparative Example 5

(77) 100 g of the polyether carbonate polyol A2 were stored in a sealed screwtop vial for 28 days at 80° C. The DMD content of the stored polyether carbonate polyol A2 was then determined.

Examples 6 and 7

(78) 100 g of the employed polyether carbonate polyol A2 were mixed with the type and amount of component K reported in table 2 and stored in a sealed screwtop vial for 28 days at 80° C. The DMD content of the stored polyether carbonate polyol was then determined in each case.

(79) TABLE-US-00002 TABLE 2 Storage tests with polyether carbonate polyol A2: Storage Storage DMD temperature time content Example Additive [° C.] [days] [ppm] 5 (comp.) — 80 28 440 6 125 ppm of phosphoric 80 28 74 acid 7 270 ppm of dibutyl 80 28 72 phosphate comp = comparative example

(80) The tests summarized in table 2 were carried out starting with polyether carbonate polyol A2 having a DMD content of 140 ppm. The results in table 2 show that the polyether carbonate polyol A2 comprising component K surprisingly has a lower DMD content after thermal storage (examples 6 and 7) and that the DMD content in the polyether carbonate polyol A2 markedly increases after thermal storage without component K (comparative example 5).

(81) Preparation of Polyether Carbonate Polyol B

(82) A nitrogen-purged 60 L pressure reactor comprising a gas metering means was initially charged with a suspension of 14.9 g of dried DMC catalyst (prepared as per example 6 of WO 01/80994 A1) and 4700 g of cyclic propylene carbonate (cPC). The reactor was heated to about 100° C. and inertized with N.sub.2 at reduced pressure (100 mbar) for 1 h. The reactor was then pressurized to 74 bar with CO.sub.2. 500 g of propylene oxide (PO) were rapidly metered into the reactor at 110° C. with stirring (316 rpm). The start of the reaction was signalled by a temperature spike (“Hotspot”) and a pressure drop. After activation the reactor was simultaneously charged with the remaining propylene oxide (33.58 kg) at 8.2 kg/h and 1.1 kg of a mixture of the starter glycerol (spiked with 180 ppm of 85% H.sub.3PO.sub.4) and monopropylene glycol (weight ratio 85/15) at 0.29 kg/h. The reaction temperature was simultaneously lowered to 105° C. The progress of the reaction was monitored via CO.sub.2 consumption while continuously controlled topping-up maintained the pressure in the reactor at the abovementioned value (74 bar). Once PO addition was complete the mixture was stirred at 316 rpm at 105° C. until no further reduction in pressure was observed. The resulting polyether carbonate polyol B was analyzed and the following result was obtained.

(83) DMD content=610 ppm

(84) CO.sub.2 content=20.4%

(85) e/f ratio=1/1.86

(86) In the following examples (comparative example 8 and examples 9 and 10) the thermal reduction in the content of volatile constituents was carried out by means of a short path evaporator.

(87) This short path evaporator was designed such that the polyether carbonate polyol B was passed from above at a temperature of 80° C. onto a vertical evaporator surface. The evaporator surface is a pipe having a centrally disposed mechanical stirrer system. This stirrer system having movable stirrer blades which brush along the heating area generated a thin film of the polyether carbonate polyol B. The volatile constituents thus evaporating (from the polyether carbonate polyol B) were condensed on an internal condenser. The necessary evaporation energy was supplied to the thin film via an external jacket.

(88) To this end, the short path evaporator was heated with an oil bath set to the temperature T1 indicated in table 3. The short path evaporator had a heating area of 0.125 m.sup.2. The temperature of the cooling spiral in the inner region of the evaporator and of the condenser upstream of the two cold traps was maintained at −10° C. using a Kryomat. The stirrer speed was 250 rpm. A vacuum of p.sub.abs=0.08 mbar, measured downstream of the two large cold traps (filled with a dry ice/acetone mixture), was achieved (Trivac rotary-vane oil pump).

(89) In each case the flow rate through the short path evaporator was 300 g of employed polyether carbonate polyol B per hour.

Comparative Example 8: Preparation of Polyether Carbonate Polyol B-1

(90) 300 g of polyether carbonate polyol B were subjected to thermal aftertreatment by short path evaporator as per the description hereinabove. The DMD content of the resulting polyether carbonate polyol B-1 was determined, see table 3.

Example 9: Preparation of Polyether Carbonate Polyol B-2

(91) 300 g of polyether carbonate polyol B were mixed (90 sec at 2300 rpm) with 125 ppm of phosphoric acid (in the form of a 40% aqueous solution). The resulting mixture was then subjected to thermal aftertreatment by short path evaporator as per the description hereinabove. The DMD content of the resulting polyether carbonate polyol B-2 was determined, see table 3.

Example 10: Preparation of Polyether Carbonate Polyol B-3

(92) 300 g of polyether carbonate polyol B were mixed (90 sec at 2300 rpm) with 210 ppm of dibutyl phosphate. The resulting mixture was then subjected to thermal aftertreatment by short path evaporator as per the description hereinabove. The DMD content of the resulting polyether carbonate polyol B-3 was determined, see table 3.

(93) TABLE-US-00003 TABLE 3 Thermal reduction in the content of volatile constituents using a short path evaporator Polyether Temperature DMD carbonate T1 content Example polyol [° C.] Component K [ppm] 8 (comp.) B-1 140 — 250 9 B-2 140 125 ppm of phosphoric <10 acid 10 B-3 140 210 ppm of dibutyl <10 phosphate comp = comparative example

(94) Table 3 shows that starting from untreated polyether carbonate polyol B mere thermal reduction in the content of volatile constituents using a short path evaporator only results in a reduction in the DMD content from 610 to 250 ppm (comparative example 8). However, addition of 125 ppm of phosphoric acid or 210 ppm of dibutyl phosphate prior to the thermal aftertreatment using a short path evaporator results in DMD values below the limit of detection which is 10 ppm (examples 9 and 10).

(95) In each of the examples which follow (example 11 (comparative) and examples 12-24) 300 g of polyether carbonate polyol B were mixed with various components K in different amounts (90 sec at 2300 rpm). The resulting mixture was then subjected to thermal aftertreatment using a short path evaporator as per the description hereinabove, the temperature T1 indicated in table 4 being established. The DMD content of the resulting polyether carbonate polyols was determined, see table 4.

(96) TABLE-US-00004 TABLE 4 Thermal reduction in the content of volatile constituents using a short path evaporator Temperature DMD T1 content Example Component K [° C.] [ppm] 11 (comp.) — 160° C. 280 12 5 ppm of phosphoric acid 160° C. 114 13 20 ppm of phosphoric acid 160° C. <10 14 35 ppm of phosphoric acid 160° C. <10 15 50 ppm of phosphoric acid 160° C. <10 16 100 ppm of phosphoric acid 160° C. <10 17 10 ppm of dibutyl phosphate 160° C. 26 18 100 ppm of dibutyl phosphate 160° C. <10 19 200 ppm of dibutyl phosphate 160° C. <10 20 400 ppm of dibutyl phosphate 160° C. <10 21 200 ppm of triethyl phosphate 160° C. 12 22 100 ppm triethyl phosphite 160° C. 34 23 100 ppm H.sub.3PO.sub.3 160° C. <10 24 200 ppm (NH.sub.4).sub.2HPO.sub.4 160° C. 14 comp = comparative example

(97) Table 4 shows that thermal treatment of the polyether carbonate polyol B using a short path evaporator (T1=160° C.) without addition of a component K only results in a reduction in the DMD content from 610 to 280 ppm (comparative example 11). However, addition of 5 ppm of phosphoric acid (example 12) or 10 ppm of dibutyl phosphate (example 17) results in a marked reduction to 114 or 26 ppm of DMD respectively. When 20 ppm of phosphoric acid are added (example 13) the DMD content is below the limit of detection (<10 ppm). Examples 21 to 24 illustrate the effectiveness of further inventive components K.

Example 25 (Comp): Reaction of Polyether Carbonate Polyol B with Chlorodiphenylphosphine with Amounts of Phosphorus Compound as Per Example 2 of U.S. Pat. No. 4,145,525

(98) The stoichiometric half of the hydroxyl end groups of the polyether carbonate polyol were reacted with chlorodiphenylphosphine. This was carried out as per example 2 of U.S. Pat. No. 4,145,525.

(99) 100 g of the polyether carbonate polyol from comparative example 25 were stored in a sealed screwtop vial for 24 h at 180° C. The DMD content of the stored polyether carbonate polyol was then determined.

(100) DMD content after storage: 1556 ppm.

(101) Preparation of Flexible Polyurethane Foams

(102) In the manner of processing by the one-stage process, which is customary for the preparation of polyurethane foams, the feedstocks listed in the examples in table 5 below were reacted with one another.

(103) Apparent density was determined to DIN EN ISO 3386-1-98.

(104) Indentation hardness was determined to DIN EN ISO 3386-1-98 (at 40% deformation and 4th cycle).

(105) Tensile strength and elongation at break were determined to DIN EN ISO 1798.

(106) The compression set at 50% deformation (CS 50%) and the compression set at 90% deformation (CS 90%) were determined to DIN EN ISO 1856. C1: trifunctional polyether polyol having an OH number of 48 mg KOH/g, produced by the DMC-catalyzed alkoxylation of glycerol with a mixture of propylene oxide and ethylene oxide in a weight fraction of 89/11, and about 8 mol % of primary OH groups. C2 Tegostab® B 2370, a preparation of organo-modified polysiloxanes from Evonik Goldschmidt C3 Addocat® 108, amine catalyst from Rheinchemie C4 Addocat® SO, tin catalyst from Rheinchemie TDI-1: Mixture comprising 80% by weight of 2,4-toluylene diisocyanate and 20% by weight of 2,6-toluylene diisocyanate having an NCO content of 48.3% by weight.

(107) As is apparent from table 5, the polyol components comprising a polyether carbonate polyol as per examples 4, 16, 18, 21, 22, 23, 24 were readily processed into flexible polyurethane foams to afford flexible polyurethane foams on the whole having a good property profile.

(108) TABLE-US-00005 TABLE 5 Preparation of flexible polyurethane foams Example 26 28 35 (comp.) 27 (comp.) 29 30 31 32 33 34 (comp.) polyol component (P) C1 parts 100.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 by wt. from example 4: A1 with parts 70.00 500 ppm of triethyl by wt. phosphate after storage*.sup.) from example 11: (comp.): parts 70.00 B after SPE.sup.#) by wt. from example 16: B with parts 70.00 100 ppm of phosphoric by wt. acid after SPE.sup.#) from example 18: B with parts 70.00 100 ppm of dibutyl by wt. phosphate after SPE.sup.#) from example 21: B with parts 70.00 200 ppm of triethyl by wt. phosphate after SPE.sup.#) from example 22: B with parts 70.00 100 ppm of triethyl by wt. phosphite after SPE.sup.#) from example 23: B with parts 70.00 100 ppm of H3PO3 by wt. after SPE.sup.#) from example 24: B with parts 70.00 200 ppm of (NH4)2HPO4 by wt. after SPE.sup.#) from example 25: (comp.): parts 70.00 B reacted with by wt. chlorodiphenylphosphine.sup.) water (added) parts 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 by wt. C2 parts 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 by wt. C3 parts 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 by wt. C4 parts 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 by wt. isocyanate component (iso) TDI-1 mixture ratio 100: 34.16 34.54 34.32 34.33 34.32 34.34 34.30 34.32 34.30 30.41 (parts by weight) P:iso = Index 108.0 108.0 108.0 108.0 108.00 108.00 108.00 108.00 108.00 108.0 Processability ok ok ok ok ok ok ok ok ok collapsed apparent density kg/m3 37.8 38.2 38.6 37.4 37.6 38.4 38.0 38.8 39.1 indentation hardness kPa 5.9 6.9 6.9 6.6 7.0 7.1 7.0 7.4 7.4 40% 1st cycle indentation hardness kPa 4.05 4.61 4.72 4.49 4.69 4.8 4.71 5.0 5.0 40% 4th cycle CS 50% % 1.8 2.0 2.3 2.0 2.2 2.1 1.9 2.0 2.2 CS 90% % 3.2 6.5 4.3 4.0 4.3 3.7 4.3 3.7 4.5 tensile strength kPa 95 121 99 106 111 112 104 115 134 elongation at break % 180 195 152 166 178 188 163 175 191 Table 5 notes: *.sup.)24 h storage at 180° C., as reported in the relevant example. .sup.#)after short path evaporator, as reported in the relevant example. comp. denotes comparative example