Composition

Abstract

An isocyanate reactive composition including at least one component selected from the group consisting of a polyether polyol, a polyester polyol, a polyether polyamide and a polyester polyamide; one or more amine components, each of said amine components having a given structure. In some embodiments, the average number of nitrogen atoms of said amine components is in the range of 5 to 10.

Claims

1. A method for reducing the emission of at least one of formaldehyde and acetaldehyde from a polyurethane or polyurea foam, by using two or more amine components as an additive in a reaction mixture to produce said polyurethane or polyurea foam, each of said two or more amine components correspond to: two or more amine components having a structure according to the formulae ##STR00017## and one or more amine components having a structure according to the formula ##STR00018## wherein R.sub.a for at least one of the amine components of formula (1) comprises 3 to 6 nitrogen atoms and R.sub.a for at least one of the amine components of formula (1) comprises 7 to 17 nitrogen atoms, R.sub.b comprises 2 to 16 nitrogen atoms and each of R.sub.a and R.sub.b independently comprises a plurality of units selected from at least one of R1, R2, and R3, combined in a random sequence, wherein: R1 is ##STR00019## R2 is ##STR00020## and R3 is ##STR00021## wherein each of R.sub.4, R.sub.5, R.sub.6 and R.sub.7 individually are —H or —CH.sub.3; and wherein the amount of the one or more amine components in the composition is between 0.05% wt and 1% wt calculated on the total weight of the composition.

2. A method 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.

3. A method according to claim 1, wherein said two or more amine components are amine components with at least one of each the following formulas ##STR00022## wherein each of R.sub.a and R.sub.b is independently a random sequence of at least one of units R1, R2, and R3, wherein R1 is ##STR00023## R2 is ##STR00024## and R3 is ##STR00025##

4. A method according to claim 1, wherein said reaction mixture comprises: at least one isocyanate component; at least one isocyanate reactive component comprising one or more reactive hydrogen atom, wherein the at least one isocyanate reactive component is selected from a polyether polyol, a polyester polyol, a polyether polyamide, and a polyester polyamide; catalysts selected from the group consisting of blowing and gelling catalysts; and optionally, fire retardants, antioxidants, surfactants, physical or chemical blowing agents, fillers, pigments, or any other typical additives used in polyurethane materials.

5. A method according to claim 1, wherein said one or more amine components is provided to the reaction mixture as part of the isocyanate reactive component.

Description

EXAMPLES

(1) An isocyanate reactive composition was provided comprising 100 gram of a glycerine initiated tri functional polyol with average MW of 6000. EO content is 15%, PO content is 85%. 4 gram water 0.1 gram N,N,N′-trimethyl-N′-hydroxyethyl bisaminoethylether; 1 gram N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; 0.4 gram diethanolamine; 0.9 gram foam stabilizer available as Tegostab B8715LF from Evonik

(2) Tegostab B 8715 LF is a low fogging siloxane based surfactant

(3) In comparative example I, no scavenger was added.

(4) In examples II and III, IV and V, respectively 0.05 w %, 0.15 w %, 0.25 w % and 0.30 w % of the ethylene amine was added, the % w based upon the weight of the reactive mixture, i.e. sum of the weights of the polyol, the polyisocyanate and all additives. In comparative example VI 0.12 w % carbalink HPC, i.e. hydroxypropyl carbamate, was added.

(5) The mixture of ethylene amine components used comprises following components: 12 w % tetraethylene pentamines (TEPA) 38 w % pentaethylene hexamines (PEHA) 22 w % hexaethylene heptamines (HEHA) 13 w % heptaethylene octamines (HEOA) 7 w % octaethylene nonamines (OENO) 8 w % molecules according to the formulae having 10 to 18 nitrogens in its structure.

(6) This mixture is hereinafter referred to as ethylene amine mixture. The average number of nitrogen atoms of ethylene amine mixture is 7.05.

(7) The average molecular weight is 270 g/mol.

(8) This isocyanate reactive compositions are reacted with 64 gram of a polymeric modified MDI variant with NCO value of 32, comprising 2,2 and 2,4 MDI between 47 and 50 w % 4,4 MDI between 56 and 60 w % pMDI between 11 and 13 w %

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

(10) The results are listed in table I.

(11) TABLE-US-00001 TABLE I Aldehydes after 5 hours/65° C. according to VDA 276 test method formaldehyde Acetaldehyde propionaldehyde Ex. products used ppb ppb ppb VDA 278 1 BLANCO 183 8 29 pass 2 Ethylene amine mixture 16 11 22 pass (0.05%) 3 Ethylene amine mixture 0 28 20 pass (0.15%) 4 Ethylene amine mixture 0 35 21 pass (0.25%) 5 Ethylene amine mixture 0 35 22 pass (0.30%) 6 CARBALINK HPC 142 11 27 no pass (0.12%)

(12) A second set of examples were prepared using the same formulation of the reaction mixture, except that following scavengers were added: Example 7: Blanco—no scavenger Example 8: scavenger triethylene tetramine (TETA)—0.15% w Example 9: scavenger tetraethylene pentamine (TEPA)—0.15% w Example 10: scavenger tetraethylene pentamine (TEPA)—0.03% w
The results are listed in table II.

(13) TABLE-US-00002 TABLE II Aldehydes after 5 hours/65° C. according to VDA 276 test method formaldehyde Acetaldehyde propionaldehyde Ex. products used ppb ppb ppb 7 BLANCO 80 4 24 8 TETA (0.15%) 0.15 22 25 9 TEPA (0.15%) 0 24 25 10 TEPA (0.03%) 76 1.5 28

(14) Similar reaction mixture as for examples 1 and 4 were prepared using the same components, however with an other ISO-index.

(15) The obtained foams were subjected to different tests to determine the influence of the scavenger on the physical properties. The results were summarized in table III.

(16) TABLE-US-00003 TABLE III 0.25% w ethylene blanco amine mixture Standard Property Index 80 Index 90 Index 80 Index 90 DIN EN ISO 845 Density (kg/m.sup.3) 82 80.1 80.8 78.9 DIN EN ISO 1856 50% compression set Init (%) 5.3 3.9 5.7 4.3 HACS (90° C./100% RH, 6.9 6.5 6.7 7.0 200 hr) (%) DIN EN ISO 3386-1 Foam hardness (40%) Init (kPa) 5.0 6.2 4.3 6.0 HA foam hardness (kPa) 3.4 4.4 3.0 4.4 Change (%) −32 −29 −31 −27 DIN EN ISO 1798 Tensile strength Init (kPa) 78.2 80.4 92.9 101.6 Dry HA (kPa) 69.9 95.1 82.4 89.4 Wet HA (kPa) 59.5 87. 78.0 96.0 Elongation Init (%) 97.6 84.3 107.0 94.4 Dry HA (%) 91.8 90.8 102.4 92.8 Wet HA (%) 127.8 129.6 133.1 133.4 DIN EN ISO 1856 50% compression set Init (%) 5.3 3.9 5.7 4.3 HACS (120° C./100% RH, 15.7 14.2 7.2 14.9 15 hr) (%) Dry HA (7 days at 140° C.) 7.1 5.6 7.3 6.5 (%)

(17) Further experiments were performed to illustrate the emission values obtained after performing the VDA 276 test method in samples according to the invention compared to samples according to the prior art.

(18) Formulations Used:

(19) 8966-10A: This is the reference foam formulation containing no primary and no secondary amines to scavenge formaldehydes in the foam. 8966-10B: In this formulation, a masterbatch according to WO2009/117479 was made. A primary amine containing compound DMAPA (=dimethylaminopropyl amine) was added to an tertiary amine (=JEFFCAT® ZF-10) in a weight ratio of 10/90. 8966-11C: In this formulation, a masterbatch according to WO2009/117479 was made. An amine compound containing at least 1 primary amine and at least one secondary amine was added to a tertiary amine (JEFFCAT® ZF-10) in a weight ratio of 10/90. 8966-10D: This formulation was made according to the invention. A compound containing at least one primary amine and at least one secondary amine is added to the isocyanate reacting mixture.

(20) 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 (3×350 grams) were taken out of the mold, crushed and put in a TEDLAR/ALU bag and sealed.

(21) The composition of the formulation used to make the foams are summarized in Table IV below.

(22) TABLE-US-00004 TABLE IV Formulation 8966-10A 8966-10B 8966-10C 8966-10D Daltocel F477 100 100 100 100 Daltocel F526 4 4 4 4 water 4 4 4 4 Jeffcat ZF10 0.1 0.1 Jeffcat DPA 1 1 1 1 Diethanolamine 0.25 0.25 0.25 0.25 Tegostab B 8734 LF2 0.9 0.9 0.9 0.9 sum 110.25 110.15 110.15 110.25 Isocyanate (MDI) 54-60 54-60 54-60 54-60 INDEX 80-90 80-90 80-90 80-90 Aldehyde scavenger blend DMAPA/Z1-10 (10/90) 0.11 aldehyde scavenger/ZF-10 (10/90) 0.11 aldehyde scavenger/Tertiary amine (80/20) 0.3 REACTIVITY String time (seconds) 80 80 80 77 End of rise (seconds) 85 85 85 83 Blow off (seconds) 85 85 85 83 observations nice nice nice nice

(23) Each foam system (3×350 grams) was then submitted to respectively the CERTIPUR and VDA 276 test method. The aldehyde emissions were measured and quantified. The emissions measured are summarized in Table V below.

(24) TABLE-US-00005 TABLE V 8966-10A 8966-10B 8966-10C 8966 10D aldehydes emissions (VDA 276) - μg/m.sup.3 at 65C/5% RH 2HR 5HR 2HR 2HR 2HR 5HR 2HR 5HR formaldehyde 239.5 190.2 205.1 179 219.5 153.6 23.6 20.6 acetaldehyde 9.4 10.4 9.29 8.91 19.5 10.6 41.9 27.5 proprionaldehyde 48 47.7 53.6 46.7 102.6 53.1 64.8 52.8 aldehydes emissions (CERTIPUR) - μg/m.sup.3 at 23C/50% RH 2HR 5HR 2HR 5HR 2HR 5HR 2HR 5HR formaldehyde 8.4 8.6 8.9 7.2 7.4 9.7 3.2 2.8 acetaldehyde 30.6 11.2 29.9 8.8 23 10.5 37.7 25.7 proprionaldehyde 91.7 45.6 98.7 42 80.2 50.8 77.7 35.5

(25) Foams submitted to the CERTIPUR emission method do NOT show a significant change in formaldehyde emissions when using formulations according to WO2009/117479. (example 8966-10B and 8966-10C)

(26) When measuring the foam emissions according to the VDA 276 method, the formaldehyde emission are seen in large quantities. On average a ten to twenty fold increase in formaldehyde is recorded compared to the emissions seen according to the CERTIPUR method.

(27) This implies that the formaldehyde must be generated/formed in the foam at these conditions. Using the formulations according to WO2009/117479 will not lower the formaldehyde emissions in the foams.

(28) The lowering of the formaldehyde emissions is seen only when employing the formulations according to the present invention (example 8966-10D)

(29) 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.