Composition to reduce the amount of aldehydes emitted from polyurethane foams

Abstract

An isocyanate reactive composition comprising At least one component selected from the group consisting of an isocyanate reactive component; a treating agent selected from the group consisting of cyclic urea substituted with at least one isocyanate reactive group, a free radical scavenger, or a polymer acid, or a mixture thereof; one or more amine components, each of said amine components having a given structure.

Claims

1. A composition comprising at least one isocyanate reactive component selected from the group consisting of a polyether polyol, a polyester polyol, a polyether polyamine and a polyester polyamine; a treating agent selected from the group consisting of (i) a cyclic urea substituted with at least one isocyanate reactive group, and (ii) a mixture of a cyclic urea substituted with at least one isocyanate reactive group and a free radical scavenger, and, optionally, a polymer acid; and one or more amine components having a structure according to one of the formulae ##STR00013## wherein Ra comprises 3 to 17 nitrogen atoms and Rb comprises 2 to 16 nitrogen atoms, and each of Ra and Rb independently comprises a plurality of units selected from at least one of R.sub.1, R.sub.2, and/or R.sub.3, combined in a random sequence, wherein: R1 is ##STR00014## R2 is ##STR00015## R3 is ##STR00016## wherein each of said R.sub.4, R.sub.5, R.sub.6 and R.sub.7 individually are H or CH.sub.3.

2. The composition according to claim 1, wherein the cyclic urea substituted with at least one isocyanate reactive group has the formula (I) or (II): ##STR00017## wherein R, R.sup.0, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are independently selected from H, OH, R.sup.11OH, NH or COOH, and R.sup.11 is a C.sub.1-C.sub.4 alkyl group, X is C, O or N with the proviso that when X is O, R.sup.3 and R.sup.4 are each zero and when X is N, one of R.sup.3 or R.sup.4 is zero, and further with the proviso at least one of R or R.sup.0 is H and that at least: one of R.sup.0, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 is OH, COOH, R.sup.11OH, or NH; or R.sup.1R.sup.2 or R.sup.5R.sup.6 are NH.sub.2.

3. The composition according to claim 1, wherein the cyclic urea substituted with at least one isocyanate reactive group is selected from the group consisting of 4,5-dihydroxy-2-imidazolidinone, 4,5-dimethoxy-2-imidazolidinone, 4-hydroxyethyl ethylene urea, 4-hydroxy-5-methyl propylene urea, 4-methoxy-5-methyl propylene urea, 4-hydroxy-5,5-dimethyl propylene urea, 1-(2-hydroxyethyl)-2-imidazolidinone or a mixture thereof.

4. The composition according to claim 1, wherein the free radical scavenger comprises a sterically hindered phenol having the formula (Ill): ##STR00018## wherein R.sup.7, R.sup.8 and R.sup.9 are independently selected from H or a C.sub.1-C.sub.10 alkyl group.

5. The composition according to claim 1, wherein the free radical scavenger is a phosphite.

6. The composition according to claim 1, wherein the free radical scavenger is a sterically hindered amine which is a substituted diphenyl amine compound having the formula (IV): ##STR00019## wherein R.sup.11 and R.sup.11 are independently selected from H or a C.sub.1-C.sub.12 alkyl or aryl group and R.sup.12 and R.sup.12 are H or a C.sub.1-C.sub.4 alkyl group in case R.sup.11 or R.sup.11 are not positioned at that place.

7. A composition according to claim 1, wherein the average number of nitrogen atoms of said one or more amine components is in the range of 5 to 10.

8. A composition according to claim 1, wherein said one or more amine components comprise at least one component comprising at least two primary and at least one secondary amine group.

9. A composition according to claim 1, wherein all R.sub.4-, R.sub.5-, R.sub.6- and R.sub.7-groups are hydrogen.

10. A composition according to claim 1, wherein the polymer acid contains at least three of the same repeating monomers, of either an unsaturated carboxylic acid or an anhydride; or wherein the polymer acid contains at least two repeating monomers, wherein the first monomer is an unsaturated carboxylic acid or an anhydride, and the second monomer is different from the first monomer.

11. A composition according to claim 1, wherein said one or more amine components is a mixture comprising triethyltetramines (TETA), tetraethyl pentamines (TEPA), pentaethylhexamines (PEHA), hexaethylheptamines (HEHA), heptaethyloctamines (HEOA) and/or octaethylenenonamines (OENO).

12. A composition according to claim 1, wherein the amount of the one or more amine components, in the composition is between 0.05% w to 1% w calculated on the total weight of the composition.

13. A composition according to claim 1, wherein the amount of the treating agent in the composition is between 0.05% w to 2.5% w calculated on the total weight of the composition.

14. A method for reducing the emission of formaldehyde and/or acetaldehyde from a polyurethane or polyurea foam, by using a composition in a reaction mixture to produce said polyurethane or polyurea foam, wherein the composition comprises: at least one isocyanate reactive component selected from the group consisting of a polyether polyol, a polyester polyol, a polyether polyamine and a polyester polyamine; a treating agent selected from the group consisting of (i) a cyclic urea substituted with at least one isocyanate reactive group, and (ii) a mixture of cyclic urea substituted with at least one isocyanate reactive group and a free radical scavenger, and, optionally, a polymer acid; and one or more amine components having a structure according to one of the formulae ##STR00020## wherein Ra comprises 3 to 17 nitrogen atoms and Rb comprises 2 to 16 nitrogen atoms, and each of Ra and Rb independently comprises a plurality of units selected from at least one of R.sub.1, R.sub.2, and/or R.sub.3,combined in a random sequence, wherein: R1 is ##STR00021## R2 is ##STR00022## R3 is ##STR00023## wherein each of said R.sub.4, R.sub.5, R.sub.6 and R.sub.7 individually are H or CH.sub.3.

15. The method according to claim 14, wherein the amount of the one or more amine components in the reaction mixture is between 0.05% w to 0.5% w calculated on the total weight of the reaction mixture.

16. The method according to claim 14, wherein the amount of the treating agent in the reaction mixture is between 0.05% w to 2% w calculated on the total weight of the reaction mixture.

17. The method according to claim 14, wherein said reaction mixture further comprises at least an isocyanate component, a catalysts selected from blowing and/or gelling catalysts, and optionally fire retardants, antioxidants, surfactants, physical or chemical blowing agents, fillers, pigments, or any other typical additives used in polyurethane materials.

18. The method according to claim 14, wherein said one or more amine components is provided to the reaction mixture as part of the isocyanate reactive component selected from the group consisting of a polyether polyol, a polyester polyol, a polyether polyamine and a polyester polyamine which is a isocyanate reactive component comprising reactive hydrogen atoms.

19. A process for making the composition according to claim 1, comprising combining a treating agent and at least one isocyanate reactive component with one or more amine components having a structure according to one of the formulae ##STR00024## wherein Ra comprises 3 to 17 nitrogen atoms and Rb comprises 2 to 16 nitrogen atoms, and each of Ra and Rb independently comprises a plurality of units selected from at least one of R.sub.1, R.sub.2 and/or R.sub.3, combined in a random sequence, wherein: R1 is ##STR00025## R2 is ##STR00026## R3 is ##STR00027## wherein each of said R.sub.4, R.sub.5, R.sub.6 and R.sub.7 individually are H or CH.sub.3; wherein: (i) the treating agent is selected from the group consisting of (i) a cyclic urea substituted with at least one isocyanate reactive group, and (ii) a mixture of cyclic urea substituted with at least one isocyanate reactive group and a free radical scavenger, and, optionally, a polymer acid; and (ii) the at least one isocyanate reactive component is selected from the group consisting of a polyether polyol, a polyester polyol, a polyether polyamine and a polyester polyamine.

20. The process according to claim 19, wherein the treating agent comprises a mixture of cyclic urea substituted with at least one isocyanate reactive group, a free radical scavenger, and a polymer acid, and wherein the polymer acid is added to the one or more amine component before adding the mixture of cyclic urea substituted with at least one isocyanate reactive group or the free radical scavenger.

Description

EXAMPLES

Example 1

(1) Several isocyanate reactive compositions are provided comprising the following ingredients as further indicated in Table 1. 100 gram DaltocelF428 supplied by Huntsman International 4 gram DaltocelF526 supplied by Huntsman International. 4 gram water 0.15 gram JEFFCAT LED-103 supplied by Huntsman International 1 gram JEFFCATDPA supplied by Huntsman International 0.25 gram diethanolamine (DELA); 0.9 gram foam stabilizer available as Tegostab B8734 LF2 from Evonik. Tegostab B 8734 LF2 is a low fogging siloxane based surfactant 0.33 gram amine componentin this example Tetraethylene pentamine (TEPA supplied by Huntsman). 0.67 gram treating agent 1e, which contains a mixture of hydroxyethyl ethylene urea and tris(dipropylene glycol) phosphite.

(2) TABLE-US-00001 TABLE 1 Overview of compounds in several compositions Foam evaluations A B E Daltocel F 428 pbw 100 100 100 Daltocel F 526 pbw 4 4 4 DELA pbw 0.25 0.25 0.25 Tegostab B 8734 LF-2 pbw 0.9 0.9 0.9 Water pbw 4 4 4 JEFFCAT LED-103 pbw 0.15 0.15 0.15 JEFFCAT DPA pbw 1 1 1 Amine component mix 9002-1-A 0.33 0.33 treating agent 1e mix 9002-1-I 0.67 Suprasec 2447 pbw 52 52 52 INDEX 80 80 80

(3) In comparative example A, no treating agent and no amine component were added.

(4) In example B, 0.33% w of the amine component as described above was added. The w % is based upon the weight of the reactive mixture, i.e. sum of the weights of the polyol, the polyisocyanate and all additives.

(5) In example E, 0.67 w % of the treating agent, which is a mixture of a cyclic urea comprising an isocyanate reactive group and a free radical scavenger, was added and 0.33 w % of an amine component according to the description above. The w % is based upon the weight of the reactive mixture, i.e. sum of the weights of the polyol, the polyisocyanate and all additives.

(6) These isocyanate reactive compositions are reacted with 52 gram of a polymeric modified MDI variant with NCO value of 32.

(7) The resulting polyurethane foams are subjected to an emission test according to VDA 276 being the test method from the Verband Der Automobil industrie.

(8) All foams were made by hand mixing the components for 5 seconds at 2000 rpm. The reacting mixture was then poured in a 6.5 liter open mold. After approximately two hours of curing at room temperature, the foams (3350 grams) were taken out of the mold, crushed and put in a TEDLAR/ALU bag and sealed.

(9) Each foam system (3350 grams) was then submitted to the VDA 276 test method. The aldehyde emissions were measured and quantified. The emissions measured are summarized in Table 2.

(10) TABLE-US-00002 TABLE 2 Overview of VDA 276 test of polyurethane made using compositions of Table 1. Foam evaluations A B E VDA 276 aldehyde emissions from foam @ 5 hr (65 C./5% RH/0.4 AE) Formaldehyde g/m.sup.3/kg foam 97 0 0 Acetaldehyde g/m.sup.3/kg foam 15 92 31 Proprionaldehyde g/m.sup.3/kg foam 54 34 54

(11) From example A it is clear that when a composition is used without an amine compound and a treating agent for making polyurethane foam the emission of formaldehyde in the foam is very high.

(12) Example B shows that when a composition comprising an amine component is used for making polyurethane foam, the emission of formaldehyde disappears or is a lot reduced. This effect was also shown in patent application with number WO2014/026802.

(13) However, it can be seen that the addition of the amine compound induces the increase of the acetaldehyde emissions in the foam.

(14) It was surprisingly found that when a composition comprises besides an amine compound, also a treating agent such as a cyclic urea substituted with at least one isocyanate reactive group and a free radical scavenger, which composition is used for making a polyurethane foam the formaldehyde emission in the foam remains very low but also the acetaldehyde increase is much less compared with using the amine compound alone (example E).

(15) In total the TVOC emissions measured according to VDA 278 remains low.

(16) It is to be understood that although preferred embodiments and/or materials have been discussed for providing embodiments according to the present invention, various modifications or changes may be made without departing from the scope and spirit of this invention.

Example 2

(17) A polyurethane foam was prepared as described in example 1 and comprises the ingredients as provided in table 3.

(18) The foam comprises Weston 430 which is a phosphite and is commercially available from Addivant LLC. The hydroxyethylene urea is commercially available from BASF, the polymer acid is a polyacrylic acid of 5000 Mw.

(19) TABLE-US-00003 TABLE 3 ingredients of PU foam Ingredients used F G H Daltocel F 428 Pbw 100 100 100 Daltocel F 526 Pbw 4 4 4 DELA Pbw 0.25 0.25 0.25 Tegostab B 8734 LF-2 Pbw 0.9 0.9 0.9 Water Pbw 4 4 4 JEFFCAT LED-103 Pbw 0.15 0.15 0.15 JEFFCAT DPA Pbw 1 1 1 TEPA Pbw 0.25 0.25 0.25 Polyacrylic acid (5000 Mw) Pbw 0.25 0.25 Weston 430 Pbw 0.5 0.5 Cyclic urea Pbw 0.5 0.5 pMDI Pbw 60 60 60 INDEX 90 90 90

(20) Table 4 provides the results of the VDA276 test of the aldehyde emission. It is clear that the combination of the amine compound with an antioxidant and cyclic urea (F), an antioxidant, cyclic urea and polymer acid (G) and polymer acid (H) provides a reduced aldehyde emission.

(21) TABLE-US-00004 TABLE 4 Aldehyde emission in PU foam Foam evaluation F G H VDA 276 aldehyde emissions from foam @ 5 hr (65 C./5% RT/0.4AE) Formaldehyde g/m.sup.3/kg foam 0 21 15 Acetaldehyde g/m.sup.3/kg foam 63 34 28