POLYURETHANE FOAMS BASED ON POLYETHERCARBONATE POLYOLS

Abstract

The invention relates to a method for producing polyurethane foams by reacting the following components A a polyol component, containing A1 40 to 100 parts by weight of polyether carbonate polyol with a hydroxyl number according to DIN 53240-1 June 2013 of 20 mg KOH/g to 120 mg KOH/g, A2 0 to 60 parts by weight of polyether polyol with a hydroxyl number according to DIN 53240-1 June 2013 of 20 mg KOH/g to 250 mg KOH/g and an ethylene oxide content of 0 to 60 wt. %, wherein the polyether polyol A2 is free from carbonate units, B B1 a catalyst and B2 optionally auxiliary and additional materials, C water and/or physical blowing agents with D di- and/or polyisocyanates, wherein the production occurs at a characteristic value of 90 to 120 and in the presence of a component K, characterised in that the component K is selected from at least one compound of the following formulas (R.sub.1)(R.sub.2)XC(O)(Y).sub.mZ (1) [(R.sub.1)(R.sub.2)XC(O)N(H)N(H)C(O)R.sub.3].sub.2 (2) [(R.sub.1)(R.sub.2)XR.sub.3C(O)N(H)].sub.2 (3), wherein m represents 0 or 1, X represents a hydroxyphenyl group, Y represents N(H), O, OR.sub.4 or C.sub.1- to C.sub.6-alkyls, Z represents H, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, wherein Z does not represent H when Y represents O, R.sub.1, R.sub.2 respectively represent H, hydroxyl, a substituted or unsubstituted C.sub.1- to C.sub.6-alkyl group or OR.sub.5, R.sub.3 represents a substituted or unsubstituted to C.sub.12-alkylene group, a substituted or unsubstituted C.sub.1- to C.sub.12-alkenylene group, R.sub.4 represents a substituted or unsubstituted C.sub.1- to C.sub.6-alkylene group, R.sub.5 represents a substituted or unsubstituted C.sub.1- to C.sub.12-alkylene group, and the component K is used in a quantity of 0.05 to 10.00 parts by weight, in relation to the sum of the parts by weight of the components A1+A2=100 parts by weight.

Claims

1. A process for producing polyurethane foams by reaction of the components A polyol component comprising A1 from 40 to 100 parts by weight of polyether carbonate polyol having a hydroxyl number in accordance with DIN 53240-1 of June 2013 of from 20 mg KOH/g to 120 mg KOH/g, A2 from 0 to 60 parts by weight of polyether polyol having a hydroxyl number in accordance with DIN 53240-1 of June 2013 of from 20 mg KOH/g to 250 mg KOH/g and a content of ethylene oxide of from 0 to 60% by weight, with polyether polyol A2 being free of carbonate units, B B1 catalysts, and B2 optionally auxiliaries and additives, C water and/or physical blowing agents, with D diisocyanates and/or polyisocyanates, where the production reaction is carried out at an index of from 90 to 120 and in the presence of a component K, wherein the component K comprises one or more compound of the following formulae
(R.sub.1)(R.sub.2)XC(O)(Y).sub.mZ(1)
[(R.sub.1)(R.sub.2)XC(O)N(H)N(H)C(O)R.sub.3].sub.2(2)
[(R.sub.1)(R.sub.2)XR.sub.3C(O)N(H)].sub.2(3) where m is 0 or 1, X is a hydroxyphenyl group, Y is N(H), O, OR.sub.4 or to C.sub.6-alkylene, Z is H, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, where Z is not H when Y is O, R.sub.1, R.sub.2 are each H, hydroxyl, a substituted or unsubstituted C.sub.1- to C.sub.6-alkyl group or OR.sub.5, R.sub.3 is a substituted or unsubstituted C.sub.1- to C.sub.12-alkylene group, a substituted or unsubstituted C.sub.1- to C.sub.12-alkenylene group, R.sub.4 is a substituted or unsubstituted C.sub.1- to C.sub.6-alkylene group, R.sub.5 is a substituted or unsubstituted C.sub.1- to C.sub.12-alkyl group, and the component K is used in an amount of 0.05 to 10.00 parts by weight, based on a sum of the parts by weight of the components A1+A2=100 parts by weight.

2. The process as claimed in claim 1, wherein component A has the following composition: A1 from 40 to 100 parts by weight of polyether carbonate polyol having a hydroxyl number in accordance with DIN 53240-1 of June 2013 of from 20 mg KOH/g to 120 mg KOH/g, A2 from 0 to 60 parts by weight of polyether polyol having a hydroxyl number in accordance with DIN 53240-1 of June 2013 of from 20 mg KOH/g to 250 mg KOH/g and a content of ethylene oxide of from 0 to 60% by weight, with polyether polyol A2 being free of carbonate units, A3 from 0 to 20 parts by weight, based on the sum of the parts by weight of the components A1 and A2, of polyether polyol having a hydroxyl number in accordance with DIN 53240-1 of June 2013 of from 20 mg KOH/g to 250 mg KOH/g and a content of ethylene oxide of 60% by weight, with polyether polyol A3 being free of carbonate units, A4 from 0 to 40 parts by weight, based on the sum of the parts by weight of the components A1 and A2, of polymer polyol, PUD polyol, PIPA polyol, or a combination thereof A5 from 40 to 0 parts by weight, based on the sum of the parts by weight of the components A1 and A2, of a polyol which is different from components A1 to A4, where the parts by weight figures for the components A3, A4 and A5 are in each case based on the sum of the parts by weight of components A1+A2=100 parts by weight.

3. The process as claimed in claim 1, wherein component A is free of components A3 and/or A4.

4. The process as claimed in claim 1, wherein component A comprises: A1 from 65 to 75 parts by weight of polyether carbonate polyol having a hydroxyl number in accordance with DIN 53240-1 of June 2013 of from 20 mg KOH/g to 120 mg KOH/g, and A2 from 25 to 35 parts by weight of polyether polyol having a hydroxyl number in accordance with DIN 53240-1 of June 2013 of from 20 mg KOH/g to 250 mg KOH/g and a content of ethylene oxide of from 0 to 60% by weight, where polyether polyol A2 is free of carbonate units.

5. The process as claimed in claim 1, wherein component A1 comprises a polyether carbonate polyol obtained by copolymerization of carbon dioxide and alkylene oxide in the presence of H-functional starter molecules, wherein the polyether carbonate polyol has a CO.sub.2 content of from 15 to 25% by weight.

6. The process as claimed in claim 1, wherein component B comprises: B1 catalyst comprising one or more of the following compounds a) aliphatic tertiary amines, cycloaliphatic tertiary amines, aliphatic amino ethers, cycloaliphatic amino ethers, aliphatic amidines, cycloaliphatic amidines, urea and derivatives of urea, and/or b) tin(II) salts of carboxylic acids, and B2 optionally auxiliaries and additives.

7. The process as claimed in claim 1, wherein component B comprises: B1 catalysts and B2 optionally auxiliaries and additives wherein component B1 comprises: B1.1 from 0.05 to 1.50 parts by weight, based on the sum of the parts by weight of the components A1 and A2, of urea and/or derivatives of urea, and B1.2 from 0.03 to 1.50 parts by weight, based on the sum of the parts by weight of the components A1 and A2, of catalyst other than those of the components B1.1, with a content of amine catalyst in the component B1.2 being not more than 50% by weight based on components B1.

8. The process as claimed in claim 1, wherein component D comprises 2,4- and/or 2,6-TDI.

9. The process as claimed in claim 1, wherein the component K comprises one or more compound of the following formulae
(R.sub.1)(R.sub.2)XC(O)(Y).sub.mZ(1)
[(R.sub.1)(R.sub.2)XC(O)N(H)N(H)C(O)R.sub.3].sub.2(2)
[(R.sub.1)(R.sub.2)XR.sub.3O(O)N(H)].sub.2(3) where m is 1, X is a hydroxyphenyl group, Y is N(H), Z is H, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R.sub.1, R.sub.2 are each H, hydroxyl or a substituted or unsubstituted C.sub.1- to C.sub.6-alkyl group, R.sub.3 is a substituted or unsubstituted C.sub.1- to C.sub.12-alkylene group, a substituted or unsubstituted C.sub.1- to C.sub.12-alkenylene group.

10. The process as claimed in claim 1, wherein the component K comprises one or more compound of the following formulae
(R.sub.1)(R.sub.2)XC(O)(Y).sub.mZ(1)
[(R.sub.1)(R.sub.2)XC(O)N(H)N(H)C(O)R.sub.3].sub.2(2) where m is 1, X is a hydroxyphenyl group, Y is N(H), Z is H, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R.sub.1, R.sub.2 are each H, hydroxyl, a substituted or unsubstituted C.sub.1- to C.sub.6-alkyl group, R.sub.3 is a substituted or unsubstituted C.sub.1- to C.sub.12-alkylene group, a substituted and/or unsubstituted C.sub.1- to C.sub.12-alkenylene group.

11. The process as claimed in claim 1, wherein the component K comprises one or more of 3-(salicyloylamino)-1,2,3-triazole, salicylamide, N,N-dodecandiol-N,N-bis(2-hydroxybenzoyl)hydrazide, and 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamyl)hydrazine.

12. The process as claimed in claim 1, wherein component K is used in an amount of from 0.5 to 6.0 parts by weight, based on the sum of the parts by weight of the components A1+A2=100 parts by weight.

13. A polyurethane foam obtained by a process as claimed in claim 1.

14. The polyurethane foam as claimed in claim 13, wherein the polyurethane foam is a flexible polyurethane foam.

15. (canceled)

Description

EXAMPLES

Test Methods

[0265] Experimentally determined OH numbers (hydroxyl number) were determined by the method of DIN 53240-1 (June 2013).

Emission DeterminationCyclic Propylene Carbonate

[0266] The quantification of the cPC content was carried out by means of .sup.1H-NMR spectroscopy (Bruker, DPX 400, 400 MHz): about 24 h after production of the flexible polyurethane foams, a sample of 1.2-1.5 g of the flexible polyurethane foam was Soxhlet extracted in acetone at 60 C. for 7.5 hours. The extract was concentrated under reduced pressure and taken up in deuterated chloroform, with dimethyl terephthalate or 1,2,4-trichlorobenzene as internal standard. The cPC content was subsequently qualified by means of .sup.1H-NMR by comparison with the internal standard.

[0267] The present invention is illustrated by the following examples, but without being restricted thereto. The symbols have the following meanings: [0268] A1-1: polyether carbonate polyol, functionality 2.8, OH number 54 mg KOH/g, 14% by weight of CO.sub.2, prepared by copolymerization of propylene oxide and carbon dioxide using glycerol and propylene glycol as H-functional starter compounds in the presence of a double metal cyanide catalyst [0269] B1-1: Niax Catalyst A-1, commercial product from Momentive Performance Materials GmbH, bis [2-(N,N-dimethylamino)ethyl]-based [0270] B1-2: Desmorapid SO, tin catalyst (from Covestro AG) [0271] B2-1: Tegostab BF 2370, commercial product from Evonik Industries [0272] C-1: water [0273] D-1: Desmodur T 80, mixture of tolylene 2,4-diisocyanate and tolylene 2,6-diisocyanate in a ratio of 80/20 (from Covestro AG) [0274] K-1: 3-(salicyloylamino)-1,2,4-triazole) (from ADEKA Polymer Additives Europe) [0275] K-2: N,N-dodecanedioyl-N,N-bis(2-hydroxybenzoyl)hydrazide) (from ADEKA Polymer Additives Europe) [0276] K-3: 1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine) (from ADEKA Polymer Additives Europe) [0277] K-4: 2,2-dihydroxy-4-methoxy-benzophenone (from Sigma-Aldrich) [0278] K-5: salicylamide (from Sigma Aldrich) [0279] Fyrol-PNX: oligomeric alkyl phosphate (from ICL-IP)

Production of Laboratory Flexible Foams

[0280] The flexible polyurethane foams described in table 1 were produced in a discontinuous process. Mixing of the components was carried out by means of a Pendraulik laboratory mixer model LM 34.

[0281] The component A1-1 (125 g) was weighed into a 500 ml paper cup together with the components B1-1, B2-1 and C-1 and premixed for 10 seconds by means of a high-speed stirrer. The component B1-2 was subsequently added and mixing was carried out for 10 seconds at the same stirring speed. Finally, the component D-1 was added to this mixture, mixing was carried out for 7 seconds and the mixture was transferred into a prepared paper box having dimensions of 20 cm20 cm15 cm.

[0282] The height of the flexible polyurethane foam blocks was about 14-15 cm. The finished flexible polyurethane foam was stored in the paper box for about 20-24 hours before it was sawn into test specimens for testing. The compressive strength and the foam density of the flexible polyurethane foams were determined in accordance with DIN EN ISO 3386-1.

[0283] When a component K was used, this was firstly stirred into the component A1-1 before the remaining formulation components as described above were added.

Production of Laboratory Box Flexible Foams

[0284] The flexible polyurethane foams described in table 2 were produced in a discontinuous process. For this purpose, the component A1-1 (2000 g) was weighed together with components B1-1, B2-1 and C-1 into a 5 1 bucket and premixed for 20 seconds by means of a high-speed stirrer. The component B1-2 was subsequently added and mixing was carried out for 10 seconds at the same speed. Finally, the component D-1 was added to this mixture, mixing was carried out for a further 7 seconds and the mixture was transferred into a prepared paper box having dimensions of 50 cm50 cm50 cm.

[0285] The height of the flexible polyurethane foam blocks was about 50-55 cm. The finished flexible polyurethane foam was stored in the paper box for about 20-24 hours before it was sawn into test specimens for testing. The compressive strength and the foam density of the flexible polyurethane foams were determined in accordance with DIN EN ISO 3386-1.

[0286] When a component K was used, this was firstly stirred into the component A1-1 before the remaining formulation components as described above were added.

Results

[0287] a) Laboratory Flexible Foams (Table 1)

[0288] Without component K, the resulting flexible polyurethane foam displayed a high emission of cyclic propylene carbonate (comparative example 1); this emission can be reduced when a PO-containing compound is used (comparative example 2). However, the addition of a component K surprisingly results throughout in lower values for cyclic propylene carbonate in the emission determination (examples 3 to 7) compared to comparative examples 1 and 2.

[0289] b) Laboratory Box Flexible Foams (Table 2)

[0290] Without component K, the resulting flexible polyurethane foam displayed a high emission of cyclic propylene carbonate (comparative example 8), with a higher emission level of cyclic propylene carbonate being found compared to the flexible laboratory foam produced on a smaller scale (comparative example 1). This emission can be reduced when a PO-containing compound is used (comparative example 9). However, the addition of a component K according to the invention surprisingly results throughout in significantly lower values for cyclic propylene carbonate in the emission determination (examples 10 to 12) compared to comparative examples 8 and 9.

TABLE-US-00001 TABLE 1 Flexible laboratory foams Example COMPONENT 1* 2* 3 4 5 6 7 A1-1 [parts by weight] 100 100 100 100 100 100 100 B1-1 [parts by weight] 0.12 0.12 0.12 0.12 0.12 0.12 0.12 B1-2 [parts by weight] 0.18 0.18 0.18 0.18 0.18 0.18 0.18 B2-1 [parts by weight] 1.20 1.20 1.20 1.20 1.20 1.20 1.20 C-1 [parts by weight] 4.50 4.50 4.50 4.50 4.50 4.50 4.50 Fyrol-PNX [parts by weight] 1.0 K-1 [parts by weight] 1.0 K-2 [parts by weight] 1.0 K-3 [parts by weight] 1.0 K-4 [parts by weight] 1.0 K-5 [parts by weight] 1.0 D-1 [parts by weight] 56.01 56.01 56.01 56.01 56.01 56.01 56.01 Index 108 108 108 108 108 108 108 Foam density kg m.sup.3 27.86 26.98 24.14 25.12 24.41 25.10 25.68 Compressive kPa 5.02 7.38 5.62 5.15 4.47 5.34 5.37 strength at 40% compression (4th cycle) Cycl. [mg/kg] 92 23 7 5 10 13 9 propylene carbonate *Comparative example

TABLE-US-00002 TABLE 2 Laboratory box flexible foams Example COMPONENT 8* 9* 10 11 12 A1-1 [parts by weight] 2000 2000 2000 2000 2000 B1-1 [parts by weight] 2.4 2.4 2.4 2.4 2.4 B1-2 [parts by weight] 3.6 3.6 3.6 3.6 3.6 B2-2 [parts by weight.] 24 24 24 24 24 C-1 [parts by weight] 90 90 90 90 90 Fyrol-PNX [parts by weight] 20 K-1 [parts by weight] 20 K-2 [parts by weight] 20 K-3 [parts by weight] 20 D-1 [parts by weight] 1120 1120 1126 1125 1122 Index 108 108 108 108 108 Foam density kg m.sup.3 22.8 22.8 22.5 22.9 23.0 Compressive kPa 4.33 4.47 4.10 4.10 3.10 strength at 40% compression (4th cycle) Cycl. [mg/kg] 562 251 32 21 76 propylene carbonate *Comparative example