SI8811711A - PROCEDURE FOR THE PREPARATION OF STABLE INGREDIENTS FROM ALL ONE CHLORFLUORALCANE AND AMINE AND / OR POLYOL CONTAINING AMINO GROUPS - Google Patents

Abstract

We propose a process for the preparation of new, stable compositions of at least one chlorofluoroalkane and an amine and/or a polyol containing amino groups, in which a combination of chlorofluoroalkanes, amines, amino alcohols and polyols containing amino groups is stabilized with 0.05 to 5 wt% of a compound where R1 and/or R2 are hydrogen, a straight or branched C1-C4-alkyl radical, a phenyl radical or a substituted phenyl radical. The products of the process are useful for the production of polyurethane foams.

Description

Process for the preparation of stable compositions of at least one chlorofluoroalkane and an amine and / or polyol containing amino groups

Technical field of the invention

C 09 K 15/06

C 08 K 5/05

C 08 L 71/00

The present invention relates to the field of organic chemical technology, specifically to a process for the preparation of novel stable compositions of chlorofluoroalkanes and amines and / or polyols containing amino groups, and are useful e.g. for the preparation of polyurethane foams.

A technical problem

There was a need to identify a technologically advanced process for the preparation of novel stable compositions of chlorofluoroalkanes and amines and / or polyols containing amino groups, and useful e.g. for the preparation of polyurethane foams, with long storage times and without the negative effects of aging.

The state of the art

In the preparation of polyurethane foams, isocyanates with polyvalent alcohols are converted into high molecular weight polymerizates containing a polyurethane-bond. When they want foamed polymerizates, they add isocyanate or polyvalent alcohol (polyol) or both, a propellant, often chlorofluoroalkane. Due to the reaction heat generated during the polymerization, the propellant is evaporated to give a low density foamed product.

If the compounds required for the preparation of the polyurethane foam material mix it directly with each other before the metabolism, they can easily produce foam with good properties. However, for practical reasons, they often keep only the diisocyanate component separately until foaming. All further components required for the preparation of the foams, such as catalysts, e.g. Araine catalysts, emulsifiers and propellants or a mixture of propellants, previously mixed with polyol.

These premixes must be such that they can be stored for long periods of use without causing breakage or decomposition, thereby impairing the quality of the foam produced.

However, this type of work is only practicable with non-amine polyols, i.e. polyols containing only carbon, hydrogen and oxygen as elements, provided that the pre-formulated mixtures are not exposed to extreme temperatures during storage. In the case of amines, aminoalcohols and polyols on an amine base, i.e. polyols containing, in addition to the aforementioned elements of carbon, hydrogen and oxygen, nitrogen and which e.g. are polyethers with amine or alkanolamine-initiated hydroxyl-free polyethers; aminbasic polyols, on the one hand, and chlorofluoroalkanes, on the other, used as propellants. This results in a decrease in pH through the formation of hydrogen chloride and in this connection a decrease in the storage stability of the liquid mixtures. In addition, the solution becomes darker, its viscosity increases, only poor quality foams are prepared, or even foam mixtures are useless.

It is now known from DE-PS 1 207 626 that to these mixtures containing aminbasic polyols in addition to chlorofluoroalkanes may be added unsaturated compounds - such as e.g. butadiene, isoprene, styrene, J-niethylstyrene or 1-alkenes with 4 to 18 carbon atoms - as stabilizers, while unsaturated oxygen-containing compounds such as e.g. vinyl acetate or methylvinyl ketones, designated as ineffective for the same purpose.

It is known from DE-PS 1 518 461 that in addition to oU-methylstyrene, anethole (= 1 - (p-methoxyphenyl) -propen-1), m-diisopropenylbenzo1, 1,1,5-triisopropenylbenzene and 1 - (p-Methoxyphenyl) -2-nitro-propene-1.

Furthermore, DE-PS 1 618 291 describes the use of p-isopropenyl-toluene (p-methyl-cL · -methylstyrene) and DE-PS 3 139 401 uses an isomeric mixture of 2,4-diphenyl-4-methylpentenes (dimer J The metabolism of amines, aminoalcohols or polyols containing amino groups with chlorofluoroalkane is inhibited.

However, it is disadvantageous that the said compounds only have relatively short storage times, and even in some cases only unsatisfactory, with their stabilizing effect. If a certain storage time is exceeded, reactions between an amine, an amino alcohol or an aminbasic polyol and chlorofluoroalkane occur again. As in the case of unstabilized mixtures, the formation of hydrogen chloride results in a decrease in pH and an increase in viscosity. The mixture becomes unwanted in color, becomes cloudy due to the hydrochloride precipitate and additionally less reactive. Such aged mixtures exhibit extended foaming time (cream time), extended gel time (gel time), and extended foaming time (foam free time). In addition, they give foams of poor quality, i.e. dark foam with uneven, often oversized cells, or even beyond use for Den preparation.

A further disadvantage is that the metals present can catalyze and accelerate the aging process, further reducing the maximum storage time in the conventional storage of pre-prepared polyol mixtures in steel or metal containers. The corrosion of the vessels, which is accelerated by the aging of the mixture, causes additional problems.

Description of solution to a technical problem with implementation examples

However, it has now been found in the present invention to solve the above problem by a process for the preparation of stable compositions of at least one chlorofluoroalkane and an amine and / or polyol containing amino groups, wherein the combination is from chlorofluoroalkanes _; such as perhalogenated C 1-6 alkanes, in particular trichlorofluoromethane, 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1, 1-trichloro-2,2,2-trifluoroethane, tetrachloro, 1,2-difluoroethane, tetrachloro- 2,2-difluoroethane and mixtures of two or more of these compounds, amines such as triethylamine, methylbis-dimethylaminoethyl-amine, N, N, N ', N'-tetramethylethylenediamine, triethylenediamine, dimethylcyclohexylamine, N, N, N', N '- tetramets 1

1,3-butanediamine, 1,1,3,3-tetramethylguanidine, 1,2,4-trimethylpiperazine, N-cyclohexylpiperidine, 4-dimethylaminopyridine,

N-methylmorpholine, morpholine, N-ethylmorpholine, N, N'-dimethylbenzylamine, N, N-dimethyl- (N, N'-dimethylamino) piperazine, N, N-dimethylpiperazine, hexadecyldimethylanine, diethylcyclohexylamine, N-phenylcycloxylamine, N-phenylcyclohexylamine, N-phenylcyclohexylamine, N-phenylcyclohexylamine, N-phenylcycloxylamine such as dimethylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, diisopropanolamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylene diamine, diethylethanolamine or 1,4-bis- (2-hydroxypropyl) 2-methylpiperazine, and polyols containing amino groups such as with amines, alkanolamines or aromatic amines initiated polyethers with a residual hydroxyl group content, such as reaction products of ethylene or propylene oxide with amines such as diethylenetriamine, ethylenediamine, triethanolamine or toluyleneamine, or amine -basic polyol having a hydroxyl number of 485 to 515 is stabilized with 0.05 to 5% by weight of a compound of formula (I)

R 'R ^! ι I <”,

HO-CH-CH 2 -C = CH 1 with respect to chlorofluoroalkane.

An effective structural unit in compounds of formula

I is a combination of a terminal double bond with a hydroxyl r group, standing with respect to this double bond in position 1 2

In Formula I, R and R, which may be the same or different, are hydrogen, a straight or branched C 1 -C 4 -alkyl radical, a phenyl radical or a lower alkyl, lower alkenyl and / or alkoxy / substituted phenyl radical.

2

Preferably R is hydrogen. R may then be hydrogen, methyl, ethyl, propyl, butyl or phenyl, e.g. also substituted by methoxy or isopropenylor phenyl. Compounds wherein R ^{1 is} hydrogen are e.g. but-3-en-1-ol, 3-methyl-but-3-en-1-ol,

3-ethyl-but-3-en-1-ol, 3-propyl-but-3-en-1-ol, 3-butyl-but-3-en-1-ol, or 3-phenyl-but-3-ene 1-ol.

1

Preferably R is methyl. R may then be hydrogen, methyl ethyl, propyl, butyl or phenyl, e.g. also methoxy or 2 isopropenyl substituted phenyl. Compounds where R is methyl are e.g. 3-methyl-but-3-en-1-ol, Vmet yl-pent-4-en-2-ol,

5-methyl-hex-5-en-3-ol, 2-methyl-hept-1-en-4-ol, 2-methyloct-1-en-4-ol, or 1-phenyl-3-methyl-but- 3-en-1-ol.

2

In a preferred embodiment, R is hydrogen and R is methyl. The compound used is then 3-roethyl-but-3-en-1-ol.

The stabilizers of formula I are used in amounts of 0.05 to 5% by weight, preferably 0.3 to 1.5% by weight, based on chlorofluoroalkane. In one embodiment of the invention, the weight fraction of e.g. 0.75% by weight of 3-methyl-but-3-en-1-ol relative to chlorofluoroalkane

In one embodiment of the present invention, compositions are stabilized with compounds of general formula (I) and have advantageous properties. The ingredients are stable for a very long time, i.e. the pH value and viscosity of the mixture only slightly change. This is true even in the presence of boiler steel and is of particular importance due to its normal storage in steel or metal containers. The resulting compositions, in their stability and good storage capacity, outperform in a known manner with conventional compounds used in the prior art stabilized compositions.

Furthermore, they are extremely suitable for the preparation of high quality foams.

To demonstrate the better effect of the compounds of formula I used as stabilizers, we compared the effect of 3-methyl-but · 3-en-1-ol with the effect of "dimeric" b-methylstyrene (known from DE-PS 3 139 401) as this is described in more detail in the examples.

The following examples further illustrate the invention but do not limit it.

- 8 EXAMPLES

For the following experiments, the composition I of the invention (containing 3-methyl-but-3-en-1-ol) and the comparative composition II (containing dimeric cL-methylstyrene) were used.

Composition no.

polyether on an amine base (mas.deli) 100.0 polysiloxane (Si-copolymer) 0.8 dimethylcyclohexylamine 2.0 Water "1.0 trichlorofluoromethane, stabilized with 0.75 wt. · ⁰ /, touches. cb-methyl-ilstirol trichlorofluoromethane stabilized with 0.75% by weight of 3-methyl-but-3-en1-ol 30.0

II

100,0

0.8

2.0

1.0

30.0

The compositions were first stored in glass vessels in the presence of boiler steel for 8 weeks at +50 ° C and then characterized by determining the parameters covered in the following table. Storage of the mixture for 8 weeks at + 50 ° C corresponds to a storage time of about 10 months at 20 ° C.

Composition no.

time I II (weeks)

value 'pH | 0 I 10,8 ! 10.9 I I f 0 1 9,2 1 1 8,5 1 viscosity (nrPa s) 0 | 123 | 120 I 8 | 138 f | 169 1 start time 0 1 17 1 17 foaming (s) (cream time) 8 1 17 1 t 30 1 foaming time (s) I 0 | 75 | 80 (gel time) | I 8 1 85 1 | 135 1 the time when it hardens 0 | 110 | 115 foam ₍ 8 | 110 | 180

Claims (1)

A process for the preparation of stable compositions of at least one chlorofluoroalkane and amine and / or polyols containing amino groups, characterized in that the combination of chlorofluoroalkanes.as a saperhalogenated C ₁ -C 2 alkanes, in particular trichlorofluoromethane, 1,1,2-trichloro- 1,2,2-Trifluoroethane, 1,1,1-trichloro2,2,2-trifluoroethane, tetrachloro-1,2-difluoroethane, tetrachlor2,2-difluoroethane and mixtures of two or more of these compounds, amines such as triethylamine, methyl- bis.dimethylaminoethyl-amine, N, NN ', Ν'-tetramethylethylenediamine, triethylenediamine, dimethylcyclohexylamine, N, N, N', N'-tram til-1,3-butanediamine, 1,1,3,3tetramethylguanidine, 1, 2,4-trimethyl-piperazine, N-cyclohexylpiperidine, 4-dimethylaminopyridine, N-methylmorpholine, morpholine, N-ethylmorpholine, N, N'-dimethylbenzylamine, N, N-dimethyl- (N, N'dimethylamino) piperazine, N. N-dimethylpiperazine, hexadecyldimethylamine, diethylcyclohexylamine, N-phenylcyclohexylamine, amino alcohols such as dimethylethanolamine, diethanolamine, Nmethyldiethanolamine, triethanolamine, diisopropanolamine, Ν, Ν, Ν'N'-t etrakis (2-hydroxypropyl) ethylenediamine, diethylethanolamine or 1,4-bis- (2-hydroxypropyl) -2-methylpiperazine, and polyols containing amino groups such as amines, alkanolamines or aromatic amines initiated polyethers with a residual hydroxyl group content, such as the reaction products of ethylene propylene oxide with amines such as diethylenetriamine, ethylenediamine, triethanolamine or toluyleneamine, or an amine-base polyol of 0.05 to which the alkyl residue, hydroxyl number 485 to 515, is stabilized with 5% by weight of a compound of the general formula ( I) R ¹ R ² II (I) HO-CH-CH, -C = CH, 1 2 R and / or R is hydrogen, a straight or branched C 1 -C 4 radical, a phenyl radical or a substituted phenyl with respect to chlorofluoroalkane.