DE2232525B2 - PROCESS FOR THE MANUFACTURING OF FLAME-RETARDANT, NON-SHRINKING, OPEN-PORED, URETHANE-CONTAINING FOAM - Google Patents

Description

R '

R ₃ SiO-J-Si-OJ-SiR ₃
O

used in which R is an aliphatic carbon hydrogen radical with less than 3 carbon atoms and R 'is a phenyl radical and in which a represents values from 0 to 3, at least 70% by weight of the mixture having the value a = 1 and compounds with a = 0 at most in proportions of 25 percent by weight, with a = 2 at most, in proportions of 20 percent by weight and with a = 3 in proportions of 5 percent by weight at most.

2. The method according to claim 1, characterized in that the polyether with at least two active hydrogen atoms and a molecular weight of 750 to 10,000, in which at least 10% of the existing OH groups are primary hydroxyl groups.

Foams containing urethane groups, the obtained by reacting polyisocyanates with polyols containing active hydrogen atoms are widely used z. B. in the field of insulation, for the production of structural elements or for upholstery purposes. The possible uses of the foamed polyurethanes are meanwhile limited by their flammability in the event of high temperatures and / or fire.

It is known that foams containing urethane groups which have flame-retardant properties, from compounds with active hydrogen atoms, preferably polyols, polyisocyanates, water and / or other blowing agents in the presence of emulsifiers, auxiliaries and catalysts as well as flame retardant Manufacture additives. The emulsifiers and stabilizers fall in the reaction mixture Task to homogenize the reactants and to start the foaming process at the same time facilitate and prevent the foams from collapsing after the gas formation has ceased. the Catalysts are intended to ensure that the processes taking place during foam formation in the desired balance and run at the right speed. A certain Flame retardancy can be achieved by adding foaming products to the starting components beforehand may be added, which will reduce the flammability of the

ίο complicate the foam. As a flame retardant Substances are compounds of phosphorus, halogens, antimony, bismuth, boron and to a certain extent of nitrogen became known. The flame retardant additives can be divided into those that be built into the foam structure due to the presence of functional groups, and into those, which, due to the lack of such groupings, are merely incorporated and more as plasticizers or Fillers have an effect (see Chapter 2.3.10 »Flame retardants Substances «, Kunststoff-Handbuch, V i e w e g - H ö c h 11 e η, Volume ViI, Polyurethane, Carl Hanser-Verlag, Munich, 1966).

The introduction of such flame retardant compounds in foams containing urethane groups with low density and large surface often causes a loss of desirable physical properties, such as good tensile strength, permanent deformation, ductility and load-bearing capacity, which makes the Application of the foam is limited. To the

jo example causes the introduction of a hygroscopic flame-retardant additive to a polyurethane foam, although a reduction in flammability, at the same time, however, the moisture absorption is increased, resulting in poor aging properties result. The use of flame retardant additives can also lead to a sharp increase of the inner cell structures, to form a coarse cell structure and / or to collapse the Lead foam. An effective fire protection of polyurethane foams in contrast to compact polyurethanes is also difficult in that a desired distribution of the additive to the Interfaces between pores and cell wall not possible due to the composition of the foam mixture is. It should also be noted that the effective fire protection of a polyurethane foam is not is just a simple function of adding various fire retardants.

Flame-retardant urethane-group foams having the desired physical properties can e.g. B. from active hydrogen atoms containing polyethers, in which at least about 10% of the existing OH groups are primary hydroxyl groups and the z. B. a molecular weight of 750 to 10,000, preferably 4,000 to 8,000, and special polyisocyanates are prepared.

So-called »modified polyisocyanates« are used as special polyisocyanates, ζ. Β. solutions of polyisocyanates containing biuret groups in

bo biuret group-free polyisoxyanates and / or solutions of at least two NCO groups and at least one Ν, Ν'-disubstituted allophanoic acid ester groupicrur.g containing polyisocyanates in allophanoic acid ester group-free polyisocyanates and / or solutions of reaction products of diisocyanates and containing divalent or polyvalent hydroxyl groups Compounds in polyisocyanates free of urethane groups and / or solutions of more than one NCO

Ur group and at least one isocyanuric acid ring: n-containing polyisocyanates in isocyanurate groups Polyisocyanates in question.

High flame resistance in foams containing urethane groups means that they are na., I der ASTM method D 1692 - 67 T as self-extinguishing are designated.

The flame-retardant, urethane group-containing foams with desirable physical properties, manufactured e.g. B. using the "modified polyisocyanates", thus have a The disadvantage is that, particularly during foaming by shaping, defects in the form of bubbles have under the foam surface, which can also propagate into the interior of the molded part. This appearance is extremely disadvantageous, e.g. B. in the manufacture of molded parts, be it for the Furniture industry or automotive industry, as this bubble formation can be clearly seen on fine upholstery fabrics emerging.

It has been shown that attempts by using commercially available polysiloxane-polyalkylene oxide copolymers to remedy the cited problem did not deliver the desired result, as an addition itself small amounts of stabilizers lead to irreversible shrinkage of the foam and therefore not recyclable foams.

Only a process for the production of flame-retardant, non-shrinking, open-pored, Found urethane group-containing foams, in which one uses certain siloxanes that the Prevent undesirable bubble formation inside the foam or under the foam surface.

The invention thus provides a process for the production of flame-retardant, non-shrinking, open-pored foams containing urethane groups and containing active hydrogen atoms Polyethers with a molecular weight of 750 to 10,000, optionally mixed with low molecular weight Compounds with active hydrogen atoms and a molecular weight up to 750 or up to 50 Percentage by weight, based on the polyether, with higher molecular weight polyesters, polyacetals, polyester amides and polycarbonates, polyisocyanates, water and / or organic blowing agents in the presence of Alkyl / phenyl siloxanes in amounts from 0.1 to 25 Wt .-% and optionally in the presence of catalysts, characterized in that as Alkyl / phenyl siloxanes a mixture of compounds of the general formula

R '

R ₃ SiO-I-Si-OI-SiR ₃
O

SiR ₃

used in the

R is an aliphatic hydrocarbon radical with fewer than 3 carbon atoms and
R 'denotes a phenyl radical, and in the
a represent values from 0 to 3, with at least 70% by weight of the mixture having the value a = 1 and compounds with a = 0 at most in proportions of 25% by weight, with a = 2 at most in proportions of 20 % By weight and with a = 3 at most in proportions of 5% by weight in the mixture.

According to GB-PS 8 96 901 are polyurethanes, including s, foamed polyurethanes, prepared by reaction of polyisocyanates with any desired hydroxy compounds, such as polyesters and polyethers, in the presence of conventional methyl / phenyl polysiloxanes. The methyl / phenyl polysiloxanes used should have improved solubility in the reaction mixture - compared to dimethyl polysiloxanes. However, the basis of the present invention is now the surprising finding that with the aid of the alkyl / phenyl-siloxane mixtures used according to the invention it is possible to prevent undesired formation of bubbles in the interior of foams and under the foam surface. The object and purpose of the present invention are therefore absolutely different from the object of the British patent

2ü was the basis. This patent specification therefore does not provide any information on how foam is produced undesirable bubble formation inside foams and under the foam surface prevent is. This problem is only solved by the method according to the invention.

Surprisingly, the following technical advantages have been shown:

1. The alkyl / phenyl-siloxanes used according to the invention are substances that deal with the Mix the listed polyethers and the other foam components very well and quickly permit. The quick and intensive mixing of the components brings considerable advantages to the in it it can be seen that the flow behavior of the

Vi reaction mixture and the nucleation of the Sehäumungsvorganges is greatly promoted, which in the case of the production of foams by shaping with long flow paths or strongly changing cross-sections is the prerequisite for optimal production, and that the stability of the reaction mixture is improved and after the foaming process a finely formed cell structure is obtained, up to the foam surface in the case of the production of foams by molding.

2. With the usual foaming conditions and recipe structure, highly elastic molded parts can be obtained with an extremely good grip, that is, the impression characteristic is

so favorably influenced.

3. The alkyl / phenyl siloxanes used according to the invention do not impair the effectiveness of auxiliaries leading to open pores, which can either be stored or chemically be installed and evenly distributed within the entire mass.

4. The siloxanes used according to the invention lead under the usual formulation structure and processing conditions to foams with high

bo flame resistance, that means they are after ASTM D 1692 - 67 T can be described as "self-extinguishing". They differ in this respect of the commonly used polysiloxane-polyalkylene oxide copolymers, which result in foams lead with the assessment "flammable" according to ASTM D 1692 - 67 T.

The known aliphatic,

Cycloaliphatic, araliphatic and aromatic ³ olyisocyanate into consideration, for example! ^ -Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate,

Cyclohexane-LS- and 1,4-diisocyanate as well as any mixtures of these isomers, l-isocyanato-S ^ .S-trimethy '.- S-isocyanatomethyl-cyclohexane,

1,3- and 5,4-phenylene diisocyanate,

2,4- and 2,6-tolylene diisocyanate

and any mixtures of these isomers, 2,4- and 2,6-hexahydrotoIuylene diisocyanate and any mixtures of these isomers, diphenylmethane ^^ '- diisocyanate. Naphthylene-1,5-diisocyanate,
Triphenylmeth? .N-4,4 ', 4 "-triisocyanate, polyphenyl-poiymethylene-polyisocyanates, as they are obtained by aniline-formaldehyde condensation and subsequent phosgenation, polyisocyanates containing carbodiimide isocyanate adducts, as described in DT-PS 10 92 007. Diisocyanates as described in US Pat. No. 3,492,330, polyisocyanates containing allophanate groups, as described in accordance with GB-PS 9 94 890, BE-PS 7 61 626 and the published Dutch patent application 71 02 524 polyisocyanates containing isocyanurate groups, as described in DT-PS 10 22 789 and 10 27 394 and in DT-OS 19 29 034 and 20 04 048, polyisocyanates containing biuret groups, as described in DT-PS 11 01 394 , in GB-PS 8 89 050 and in FR-PS 70 Π 514, polyisocyanates produced by telomerization reactions, as described in BE-PS 7 23 640, ester group-containing polyisocyanates according to GB-PS 9 56 474 and 10 72 956, also aliphatic, cycloaliphatic, araliphatic or aromatic polyisocyanates, as they are mentioned by W. S iefge η in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, reaction products of the abovementioned polyisocyanates with acetals according to DT -PS 10 72 385 and polyisocyanates, as they are mentioned in DT-PS 10 22 789 and 10 27 394.

It is of course also possible to add any desired mixtures of the abovementioned polyisocyanates use.

The technically easily accessible polyisocyanates, eg. B. that 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers and polyphenylpolymethylene polyisocyanates, as produced by aniline-formaldehyde condensation and subsequent phosgenation will.

According to the invention, the preferred polyisocyanates are solutions of so-called "modified polyisocyanates", (i.e. solutions of polyisocyanates containing biuret, allophanate, urethane or isocyanurate groups contained in "unmodified polyisocyanates", i. H. free from biuret, allophanate, urethane or isocyanurate groups Polyisocyanates are used. The production of these "modified polyisocyanates" is on known. The solutions generally have a content of 5 to 85% by weight, preferably 10 to 50% % By weight, of "modified polyisocyanate". The "unmodified polyisocyanates" are mainly toluene-2,4- and / or 2,6-diisocyanate, optionally in a mixture with 4,4'-dipehnylmethane diisocyanate, in question. The production of the allophanate polyisocyanals can ζ. B. be carried out according to BE-PS 7 63 529, wherein Diisocyanates such as toluene-2,4-diisocyanate or mixtures the same with toluene-2,6-diisocyanate are preferably used. Their solutions usually have a content of 5 to 85% by weight, preferably 10 to 50% by weight, of allophanate polyisocyanate.

Examples of solutions of "modified polyisocyanates" are also solutions of biuret groups Polyisocyanates in polyisocyanates free of biuret groups. Of these, 5 to 85% by weight are preferred Solutions of polyisocyanates containing biuret groups of the general formula

Il

OCN-R-N-CNR-NCO
OCN-RNC = OX

in which R is a Q- to Cio-alkylene radical, Cs- to Cio-cycloalkylene radical, C ₇ - to C | _2- aralkylene radical or C ₆ to Cio-arylene radical and X is hydrogen or the grouping

= \ <^ U IN J _n H

R-NCO

means in which R has the meaning already mentioned and η is an integer from 0 to 5, in biuret group-free polyisocyanates, the proportion of biuret polyisocyanates with more than 3 isocyanate groups, based on the total amount of polybiuret isocyanates, being at least 20% by weight . The preparation of polyisocyanates containing biuret groups is described, for example, in GB-PS 8 89 050 and in DT-PS 1101394. Solutions of polyisocyanates containing biuret groups, which have been prepared either by reacting 2,4- and / or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate or a polyisocyanate mixture obtained by aniline-formaldehyde condensation and subsequent phosgenation with water or formic acid are, in biuret group-free polyisocyanates are preferred.

Also containing 0.03 to 5% by weight, preferably 0.1 to 2% by weight, chemically bound emulsifiers Polyisocyanates are suitable. These emulsifiers should be -OH, amino-, amido-, COOH-, -SH- or Urethane groups have and are therefore by reaction with the isocyanate groups in the Polyisocyanate incorporated (cf. DT-OS19 63 189).

It is also possible to use solutions of polyisocyanates containing urethane groups containing polyisocyanates, the urethane-containing polyisocyanates optionally have a higher degree of branching than pure difunctional isocyanates. The solutions have a content of urethane group-containing polyisocyanates from 5 to 85%, preferably from 10 to 50%, and the remainder consists of polyisocyanates free of urethane groups.

Solutions of at least one isocyanuric acid ring are also used as "modified polyisocyanates" containing polyisocyanates are used in liquid polyisocyanates free of isocyanurate groups. Such

Polyisocyanates containing isocyanurate groups and Process for their production are, for. B. in DT-PS 9 51 168 and 10 22 789, in GB-PS 8 21 158.8 27 120, 8 56 372, 9 27 173, 9 20 080 and 9 52 931, in US-PS 31 54 522, 28 01 244, in FR-PS 15 10 342 and the BE-PS 7 18 994. As polyisocyanates, which have at least one isocyanuric acid ring, come preferably the polymers of 2,4- or 2,6-tolylene diisocyanate or any mixtures of these isomers, optionally mixed with 4,4'-diphenylmethane diisocyanate in question. The solutions are obtained by adding the isocyanurate groups Polyisocyanate usually in amounts of 5 to 85 wt .-%, based on the weight of the resulting Polyisocyanate solutions, in the liquid free from isocyanurate groups Polyisocyanate dissolves.

As polyisocyanates free of urethane groups, allophanate groups, isocyanurate groups and biuret groups aliphatic, cycloaliphatic, aromatic or araliphatic polyisocyanates can be used, how they z. B. in Liebigs Annalen der Chemie, Volume 562 (1949), page 775 ff., Are described. Preferably are 2,4- and / or 2,6-tolylene diisocyanates or the undistilled isomer mixtures, diphenylmethane-4,4'- and / or 2,4'-diisocyanate or not distilled crude products, naphthalene-l, 5-diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, 1 -isocyanato-S.S.S-trimethyl-S-isocyanato-methyl-cyclohexane, by condensation of aniline and / or alkyl-substituted anilines with formaldehyde and subsequent phosgenation obtained polyphenylpolymethylene polyisocyanates and carbodiimide isocyanate adducts Isocyanates such as are used, for. B. in DT-PS 10 92 007 are used.

The polyethers used as starting material for the process according to the invention have a molecular weight from 750 to 10,000. Polyethers are preferably used in which at least 10% of the existing hydroxyl groups are primary OH groups. The polyethers are z. B. by implementing Compounds with reactive hydrogen atoms, such as. B. polyalcohols, with alkylene oxides, such as Ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin, and possibly later Modification of the purchased polyethers with ethylene oxide. Suitable connections with reactive hydrogen atoms are polyalcohols and polyphenols, e.g. B.

Ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1.6 hexanediol. Decanediol-1,10, butyne-2-diol-1,4, Glycerine, butanediol-2,4, hexanetriol-1,3,6, Trimethylolpropane, resorcinol,

Di-tert-butyl catechol,

2-hydroxy-2-naphthol, 6,7-dihydroxy-1-naphthaol, 2,5-dihydroxy-1-naphthol,

2,2- (p-hydroxyphenyl) propane, 4- (p-hydroxyphenyl) methane, tris (hydroxyphenyl) alkanes, such as Tris (hydroxyphenyl) methane and tris (hydroxyphenyl) propane.

Other suitable polyethers are the adducts of 1,2-alkylene oxides with mono- or aliphatic polyamines or of an aromatic nature, such as methylamine, ethylenediamine,

Tetra- or hexamethylenediamine, diethylenetriamine, aminoethylpipcrazine, Toluidine, o-, m- and p-phenylenediamine,

2,4- and 2,6-diaminotoluene, 2,6-diamino-p-xylene
and polynuclear and condensed aromatic
Polyamines, like

1,4-naphthylenediamine and 4,4'-diaminoazobenzene. Also the adducts of 1,2-alkylene oxides with ethanolamine, diethanolamine, methyl diethanolamine. Triethanolamine and ammonia are suitable. Resin-like materials of phenol are also used as starting media and resol type in question.

κι All of these polyethers are preferably used built up of ethylene oxide. The polyethers mentioned can also be converted into less modified as equivalent amounts of polyisocyanate.

The higher molecular weight polyethers to be used according to the invention can also be mixed with low molecular weight compounds (molecular weight up to 750) with active hydrogen atoms or in Mixture with up to 50% by weight, based on the polyether, with higher molecular weight polyesters, polyacetals, Polyester amides and polycarbonates can be used. As low molecular weight compounds with active hydrogen atoms are mainly compounds containing hydroxyl groups in question, z. B. Ethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, Glycerine, trimethylolpropane, castor oil or adducts (molecular weights usually from 200 to 750) of alkylene oxides, such as. B. ethylene oxide, propylene oxide or butylene oxide to such low molecular weight j «compounds with active hydrogen atoms or an Water.

The production of the self-extinguishing polyurethane foams takes place after the prepolymer or preferably by the known one-shot process. Foam is manufactured using the one-shot process at room temperature and / or elevated temperature by simply mixing the starting materials, where appropriate, emulsifiers and other auxiliaries can also be used. 4ü It is advantageous to use machines here Facilities such as B. in FR-PS 10 47 713 are described.

The following emulsifiers and auxiliaries are to be mentioned:
Suitable emulsifiers are, for. B. ethylene oxide or ethylene oxide / propylene oxide adducts with hydrophobic hydroxyl or amino groups or amido groups-containing substances.

As Ketalysatoren for the production of foams z. For example, tertiary amines and / or silaamines, 5 (used i N-substituted aziridines and hexahydrotriazines, optionally in combination with organic metal compounds. While the amines preferably the blowing reaction catalyzing effect the organic metal compounds preferably on the Vernctzungs- v> reaction. For To achieve reaction times that are favorable in terms of foaming technology, the amount of catalyst to be used is empirically determined as a function of the particular constitution of the catalyst or catalyst mixture chosen

Dimethylbenzylamine, N-methylmorpholine,
Triethylcinediamine, dimethylpipcra / .in,
hl 1,2-dimethylimidazole, dimethyldithanolumin,
Diethanolamine, triethanolamine,
Diethylaminoethanol,
Tetramethyl-u-butaninemin,

13th

N-methyl-N'-dimethyl-aminoethyl-piperazine and Pentamethylene triamine.

Silaamines are silicon compounds that contain carbon-silicon bonds, such as she z. B. in DT-PS 12 29 290 are described. As examples, there may be mentioned 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyltetramethyldisiloxane. It but also nitrogenous bases such as tetraalkylammonium hydroxides and alkalis are used as catalysts, Alkali phenolates or alcoholates, such as sodium methylate, are suitable. If necessary in combination with amines, silaamines and the hexahydrotriazines known from DT-OS 17 69 043 used organic metal compounds are preferably organic tin compounds, e.g. B. Tin (II) octate or dibutyl tin dilaurate.

Additives are also organic or inorganic fillers and dyes or plasticizers, such as Phthalic acid ester.

The foaming is preferably carried out in molds. The reaction mixture is introduced into a mold. Metal, e.g. B. aluminum or plastic, e.g. B. epoxy resin in question. The foamable reaction mixture foams up in the mold and forms the molded body. The J3 pre-foaming can be carried out in such a way that the molded part has a cell structure on its surface, but it can also be carried out in such a way that the molded part has a compact skin and a cellular core. In the latter case, one can proceed as m, that as much foamable in the form of reaction mixture enters, that the foam formed just fills the mold. One can also operate such that more foamable reaction mixture enters into the mold than is necessary to fill the y Forminncren with foam. Such a procedure is e.g. B. from US-PS 11 78 490 or 31 82 104 known.

In pre-foaming, release agents known per se are often also used. 4i

Cold-curing foams, in particular, are produced by the process according to the invention (cf. G B-PS 11 62 517 and DT-OS 21 53 086).

The alkyl / phenyl siloxanes used in the process according to the invention are known and can z. B. by the method of DT-PS 10 46 049 or US-PS 30 12 052 are produced.

The foams produced according to the invention can be used in known applications, in particular in the upholstery sector. -,

The alkyl / phenyl siloxanes used in the examples below represent a mixture of compounds of the general formula given, where R is a methyl radical and R 'is a Means phenyl radical. They have the following composition:

Alkyl / phenyl siloxane 1
83.5 parts by weight of a compound of the general formula with the value a - \

14.5 parts by weight of a compound of the general

Formula with the value «1 ■■ = 2

2.0 parts by weight of a compound of the general formula with the value a = 3.

Alkyl / phenyl siloxane 2

15.0 Weight parts of a compound of general Formula with the value. '/ = 0 71.0 parts by weight of a compound of the general

Formula with the value a = 1
12.3 parts by weight of a compound of the general

Formula with the value a - 2
1.7 parts by weight of a compound of the general formula with the value a = 3.

Alkyl / phenyl siloxane 3

25.0 parts by weight of a compound of the general

Formula with the value a = 0
74.0 parts by weight of a compound of the general

Formula with the value a = 1
1.0 part by weight of a compound of the general formula with the value a = 2.

Example 1 A) Preparation of the polyisocyanate

To a mixture of 225 parts of a mixture of 80 wt .-% 2,4 wt .-% and 20 to 2,6-toluene diisocyanate and 274 parts of 4,4'-diphenylmethane diisocyanate at 60 ^c C, 20 parts of 1,2-propylene glycol added and brought to reaction for 30 minutes. After the addition of 1 part of jS-Phenyläthyläthylenamin is heated to 130 ⁰ C. The trimerization taking place at this temperature is stopped after 2½ hours at an NCO content of the reaction mixture of 26.5% by adding 1 part of methyl p-toluenesulfonate. After dilution with 624 parts of an 80/20 mixture of 2,4- and 2,6-toluylene diisocyanate, a polyisocyanate solution is obtained which, by the values of NCO content (%): 38.4, viscosity cP ₂ 5 ° e: 24, Refractive index nf: 1.5738 is marked.

B) Manufacture of the foam

100 parts by weight of one started on dipropylene glycol Polypropylene glycol, which was modified with ethylene oxide, that terminal 60% primary Hydroxyl groups with an OH number of 28 resulted,

3.5 parts by weight of water

0.1 part by weight of endoäthylenpiperazine 0.4 part by weight of triethylamine 0.9 parts by weight of the alkyl / phenyl siloxane 1

are mixed together and with 47.0 parts by weight of the polyisocyanate listed under A) Brought reaction. A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 38 Tensile test according to DIN 53 571 (kp / cm ² ) 0.8 Elongation at break according to DIN 53 571 (%) 150 Compression test according to DIN 53 577 (p / cm ² ) 25th Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 6.0 Mean time to extinguish (sec.) 35 judgement self- vcrselete c

Example 2 A) Preparation of the polyisocyanate

27.5 parts of the mixture mentioned in Example 1 ve 2,4- and 2, fi-toluylene diisocyanate are at 60 "C m 1.33 parts of 1,2-propylene glycol and after 30 minutes Response time, during which the approach to 80 °

heated, mixed with 0.044 parts of jU-Phenyläthyläihylenimiri. Under nitrogen as protective gas is now heated to 13O ⁰ C and the trimerization after about 5 hours reaction time at this temperature, stopped by the addition of 0.042 parts of benzoyl chloride at a "> NCO value of 25.8%. After diluting the reaction mixture with 71.50 Parts of a 65/35 mixture of 2,4- and 2,6-toluylene diisocyanate are added to this solution with 5.28 parts of 2,3-dibromopropanol and reacted for 2 hours at 80 to 90 ^° C. The modified polyisocyanate solution is characterized by the values of NCO content (%): 38.5, viscosity cP25 ° c: 26 and refractive index n ^s $: 1.5690.

B) Manufacture of the foam

100 parts by weight of a started on Dioxydiphenylmethan polypropylene glycol, with ethylene oxide was modified so that at the end approx. 60% primary OH groups with an OH number of 28 resulted.

3.5 parts by weight of water

0.1 part by weight of endoethylene piperazine

1.0 part by weight of N, N-dimethylbenzylamine

1.0 part by weight of alkyl / phenyl siloxane 1

2 j

are mixed together and with 44.0 parts by weight of the polyisocyanate prepared under A) for Brought reaction. A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ )
Tensile test according to DIN 53 571 (kp / cm ² )
Elongation at break according to DIN 53 571 (%)
Compression test according to DIN 53 577 (p / cm ² )
Flammability according to
ASTM D 1692-67 T
Burning distance / mean value (cm)
Mean time to extinguish (sec.)
judgement

BeisDiel 3

40

0.7
160
25th

3.5
25th

self-extinguishing

A) Preparation of the polyisocyanate

25.0 parts of the mixture of 2,4- and 2,6-tolylene diisocyanate mentioned in Example 1 are added at 22.degree 0.040 part of a solution of water in acetone (25 g of water, made up to 1000 ml with acetone) and 0.038 Parts of j3-Phenyläthyläthylenimin added. After a short incubation period, the slightly exothermic begins Trimerization of the diisocyanate, which after a reaction time of about 2 to 2 '/ 2 hours at a NCO content of 31% and a reaction temperature of now 70 ° C by adding 0.024 parts methyl p-toluenesulfonate is stopped. at a temperature of the reaction mixture of 80 ° C. 3 parts of tripropylene glycol are added to this and for IV2 hours at the same temperature Implementation brought.

After addition of 75 parts of 80/20 mixture of 2,4- and 2,6-diisocyanate and intensive homogenization of the reaction components are 5.42 parts of 2,3-dibromopropanol added to the batch at 90 ⁰ C. After 2stündigcr reaction time at 90 to 100 ⁰ C, the Polyisocyanatkombination is characterized by NCO content (%): 38.2, viscosity CLV ι, ■: 33 and refractive index η · '". 1.5790

B) Manufacture of the foam

100 parts by weight of a propylene glycol started polypropylene glycol, which with ethylene oxide so was modified so that at the end approx. 60% primary hydroxyl groups with an OH number of 28 resulted.

3.2 parts by weight of water

0.1 part by weight of endoethylene piperazine

0.4 parts by weight of triethylamine

1.0 part by weight of alkyl / phenyl siloxane 2

are mixed with one another and reacted with 45.5 parts by weight of the polyisocyanate prepared under A).
A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 35

Tensile test according to DIN 53 571 (kp / cm ² ) 0.6

Elongation at break according to DIN 53 571 (%) 135

Compression test according to DIN 53 577 (p / cm ² ) 20
Flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 6.0

Average time to extinguish (sec.) 35

Self-extinguishing assessment

ίο B e i s ρ i e 1 4

A) Preparation of the polyisocyanate

35.0 parts of the mixture of 2,4- and 2,6-tolylene diisocyanate mentioned in Example 1 are used at 60.degree

Γ) 1.96 parts of 1,2-propylene glycol are added and during 30 Brought minutes to the reaction, the reaction mixture heated to 80 ° C. After adding of 0.037 parts of 0-Phenyläthyläthylenimin is on 130 ° C and heated at this temperature, at the one The isocyanate mixture is trimerized and left on until an NCO value of 30.0 is reached, which is approx. Taken for 1 to 2 hours. After cooling to 100 ° C., 3.70 parts of tripropylene glycol are added and in the course of 1 hour at the same temperature

■ Γ) implemented. Which after this time through The reaction mixture, which has an NCO value of 23.3%, is now 65.06 parts of an 80/20 mixture diluted by 2,4- and 2,6-tolylene diisocyanate. The polyisocyanate solution obtained has the following

• -χι values: NCO content (%): 38.9, viscosity CP ₂ -, <. ·: 39, refractive index: n ^! "": 1.5642.

B) Manufacture of the foam

100 parts by weight of a trimethylolpropane ■ vi started polypropylenetriol, the so with ethylene oxide was modified so that at the end approx. 60% primary hydroxyl groups resulted with an OH number of 28,

2.6 parts by weight of water
0.15 part by weight of endoethylene piperazine
0.40 parts by weight of tetramethylethylenediamine
2.0 parts by weight alkyl / phenyl-siloxane 3

are mixed together and with 38.8 Gewichsiei - (/> len of the polyisocyanate listed under A) reacted.

A foam with the following mechanical properties is obtained Characteristics:

Density according to DIN 53 420 (kg / m ³ )
Tensile test according to DIN 53 571 (kp / cm ² )
Elongation at break according to DIN 53 571 (%)
Compression test according to DIN 53 577 (p / cm ² )
Flammability according to
ASTM D 1692-67 T
Burning distance / mean value (cm)
Mean time to extinguish (sec.)
judgement

41

0.6
135
20th

4.1
30th

self-extinguishing in

Example 5
A) Preparation of the polyisocyanate

The procedure is the same as described under 4 A), except that 2.03 parts of trimethylolpropane are used instead of tripropylene glycol and the reaction mixture is diluted with 66.30 parts of an 80/20 mixture of 2,4- and 2,6-tolylene diisocyanate, see above a polyisocyanate solution with the values: NCO content (%): 39.0, viscosity cP25 ° c: 58, refractive index n ^s S : 1.5682 is obtained.

B) Manufacture of the foam

100 parts by weight of a started on trimethylolpropane polypropylenetriol, the so with ethylene oxide was modified so that at the end approx. 70% primary hydroxyl groups with an OH number of 32.0 result-

2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine, 1.0 part by weight of N, N-dimethylbenzylamine

1.5 parts by weight of alkyl / phenyl siloxane 2

are mixed together and with 37.5 parts by weight of the polyisocyanate prepared under A) brought to the j5 reaction. A foam is obtained with the following mechanical properties:

40

4th

Density according to DIN 53 420 (kg / m ³ ) 42 Tensile test according to DIN 53 571 (kp / cm ² ) 0.6 Elongation at break according to DIN 53 571 (%) 140 Compression test according to DIN 53 577 (p / cm ² ) 22nd Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 4.0 Mean time to extinguish (sec.) 40.0 judgement self going out

Example 6
A) Preparation of the polyisocyanate

38.46 parts of tolylene-2,4-diisocyanate are mixed in a mixer tank under nitrogen as protective gas at 6O ⁰ C and 1.54 parts of 1,2-propylene glycol and placed for 30 minutes for reaction, wherein r> the reaction mixture without heat supply heated at 95 to 100 ⁰ C. After the addition of 0.060 parts of 0-PhenyläthyläthylenimJn is heated to 130 ^c C and at this temperature so long left in place until after about 5 to 6 hours, an NCO value of 26.0% is reached. The w> trimerization of the polyisocyanate will now by adding 0.038 parts of p-Toluolsulfonsäurcmcthylester stopped and the mixture, after cooling to 12O ⁰ C and 60.0 parts of 80/20 mixture of 2,4- and 2,6-diisocyanate diluted Polyisocyanate μ is characterized by the following values: NCO-Gchalt (%): 39.4, viscosity clVt ·: 63, refractive index nl °: 1.5721.

B) Manufacture of the foam

100 parts by weight of a polypropylene triol started on hexanetriol and modified with ethylene oxide it was found that at the end 60% primary hydroxyl groups resulted with an OH number of 35,

2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine

0.4 parts by weight of triethylamine

0.2 part by weight of tetramethylethylenediamine

1.0 part by weight of alkyl / phenyl siloxane 1

are mixed together and 37.0 parts by weight of the polyisocyanate prepared under A) for Brought reaction. A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 42

Tensile test according to DIN 53 571 (kp / cm ² ) 0.6

Elongation at break according to DIN 53 571 (%) 130

Compression test according to DIN 53 577 (p / cm ² ) 22
Flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 4.0

Average time to extinguish (sec.) 45.0

Self-extinguishing assessment example 7

A) Preparation of the polyisocyanate

0.061 parts of a solution of water in acetone are added to 38.76 parts of toluylene-2,4-diisocyanate at 25.degree (25 g of water, made up to 100 ml with acetone) and 0.058 part of j3-phenylethyleneimine were added. To The slightly exothermic trimerization of the diisocyanate begins after a short incubation period, which occurs after approx. 2 hours is stopped at an NCO value of 31.0 to 31.3% by adding 0.042 part of benzoyl chloride.

The reaction mixture is now brought to 8O ⁰ C and treated with 2.33 parts of tripropylene glycol over 10 to 15 minutes, maintaining a reaction temperature of 95 to 100 ⁰ C is reached. Without further supply of heat, the mixture is stirred for 1 hour and then diluted with 58.91 parts of a mixture of 2,4- and 2,6-tolylene diisocyanate (80: 20% by weight). The solution of the modified isocyanurate polyisocyanate in toluene diisocyanate is characterized by the following values: NCO content (%): 39.5, viscosity CP ₂ SC-: 54, refractive index π ??: 1.5827.

B) Manufacture of the foam

100.0 parts by weight of a polypropylenetriol started on trimethylolproparar, which se with ethylene oxide has been modified so that it results in 60% primary hydroxyl groups at the end with an OH number of 35.0 th.

2.5 parts by weight of water

0.1 parts by weight of endoethylene piperazine

0.8 parts by weight of triethylamine

2.0 parts by weight of alkyl / phenyl siloxane 2

are mixed together and 37.5 parts by weight of the polyisocyanate listed under A) Brought reaction. A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ^J ) 43

Tensile test according to DIN 53 571 (kp / cm ² ) 0.6

Elongation at break according to DIN 53 571 (%)

Di ückvci'süch ii according to DIN 53 577 (p / cm ² )

Flammability according to

ASTM D 1692-67 T
Burning distance / mean value (cm)
Mean time to extinguish (sec.)
judgement

135
25th

4.0
42.0
self-extinguishing

Density according to DIN 53 420 (kg / m ³ ) 43 Tensile test according to DIN 53 571 (kp / cm ² ) 0.7 Elongation at break according to DIN 53 571 (%) 130 Compression test according to DIN 53 577 (p / cm ² ) 22nd Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 3.0 Mean time to extinguish (sec.) 25.0 judgement self going out

Example 9
A) Preparation of the polyisocyanate

To a mixture of 225 parts of a mixture of 80 wt .-% 2,4 wt .-% and 20 2,6-diisocyanate and 275 parts of 4,4'-diphenylmethane diisocyanate are at 6O ⁰ C, 20 parts of 1,2-propylene glycol added and brought to reaction for 30 minutes. After the addition of 1 part 0 Phenyläthyläthylenimin is heated to 130 ⁰ C. The trimerization taking place at this temperature is stopped after 2 1/2 hours at an NCO content of the reaction mixture of 26.5% by adding 1 part of methyl toluenesulfonate. After dilution with 624 parts of an 80/20 mixture of 2,4- and 2,6-toluylene diisocyanate, a polyisocyanate solution is obtained which has the values of NCO content (%): 38.4, viscosity CP ₂ SC = 24, refractive index n ^s o °: 1.5738 is marked.

Example 8
A) Preparation of the polyisocyanate

95 parts of the modified isocyanurate polyisocyanate described in Example 4 in toluene diisocyanate are mixed with 5 parts of 2,3-dibromopropanol ^{at 90 ° C. and reacted at this temperature for 2 hours.} The resulting polyisocyanate solution is characterized by the values of NCO content (%): 36.0, viscosity cP ₂₅ ° c: 81, refractive index π?: 1.5858.

B) Manufacture of the foam

100.0 parts by weight of a glycerine-started polypropylene triol which is modified with ethylene oxide in this way it was found that at the end 60% primary hydroxyl groups resulted with an OH number of 35.0,

2.5 parts by weight of water
0.1 part by weight of endoethylene piperazine
0.5 part by weight of tetramethylethylenediamine
1.8 parts by weight of alkyl / phenyl siloxane 3

are mixed together and mixed with 37.5 parts by weight of the polyisocyanate prepared under A) Brought reaction.

A foam with the following mechanical properties is obtained:

100.0 parts by weight of a sorbitol-started polypropylene hexol that is modified with ethylene oxide in this way it was found that more than 10% primary hydroxyl groups resulted at an OH number of 35,

2.5 parts by weight of water
0.1 part by weight of endoethylene piperazine
0.3 parts by weight Ν, Ν-Dimethylbenzylamiii
2.0 parts by weight of alkyl / phenyl siloxane 1

are mixed together and mixed with 34.5 parts by weight of the polyisocyanate listed under A) Brought reaction.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 45 Tensile test according to DIN 53 571 (kp / cm ² ) 0.5 Elongation at break according to DIN 53 571 (%) 160 Compression test according to DIN 53 577 (p / cm ² ) 20th Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 4.5 Mean time to extinguish (sec.) 42.0 judgement self going out

Example 10

A) Preparation of the polyocyanate

38.46 parts of tolylene-2,4-diisocyanate are used in a mixer tank under nitrogen as protective gas at 60 ⁰ C with 1.54 parts of 1,2-propylene glycol and mixed for 30 minutes, allowed to react, with the reaction mixture without heating to 95 heated to 100 ^{0 C.} After the addition of 0.060 parts of beta-Phenyläthyläthylenimin is heated to 130 ⁰ C and sized at that temperature until after about 5 to 6 hours, an NCO value of 26.0% is reached. The trimerization of the polyisocyanate is now stopped by adding 0.038 part of methyl p-thiolsulfonate and, after cooling to 120 ° C., the batch is diluted with 60.0 parts of an 80/20 mixture of 2,4- and 2,6-tolylene diisocyanate. The reaction mixture is characterized by the following values: NCO content (%): 39.4, viscosity cP ₂₅ -c: 63, refractive index: π! ⁰ : 1.5721.

B) Manufacture of the foam

100 parts by weight of a started on trimethylolpropane polypropylenetriol, the so with ethylene oxide was modified so that at the end approx. 40% primary hydroxyl groups with an OH number of 20 resulted.

2.5 parts by weight of water
^h0 0.20 parts by weight of endoethylene piperazine

0.3 part by weight of N, N-dimethylbenzylamine
1.2 parts by weight of alkyl / phenyl suloxane 1

are mixed together and with 35.0 weight b5 share of the polyisocyanate listed under A) brought to the reaction.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 240 (kg / m ³ ) 45 Tensile test according to DIN 53 5/1 (kp / cm ² ) 0.6 Elongation at break according to DIN 53 571 (%) 130 Compression test according to DIN 53 577 (p / cm ² ) 25th Flammability according to \ STMD1692-67T Burning distance / mean value (cm) 5.0 Mean time to extinguish (sec.) 30.0 judgement self going out

Example 11

KX) parts by weight of a dipropylene glycol started polypropylene glycol, the so with ethylene oxide was modified so that at the end 60% primary i:> hydroxyl groups resulted with an OH number of 28,

3.5 parts by weight of water

0.1 part by weight of endoethylene piperazine

0.6 parts by weight of triethylamine

1.2 parts by weight of alkyl / phenol-siloxane 1

are mixed with one another and treated with 45.5 parts by weight of a polyisocyanate containing biuret groups, which by reacting a mixture of r> 2,4- and 2,6-tolylene diisocyanate in an isomer ratio of 65:35 percent by weight and water has been produced (NCO content 38.5%) for Brought reaction.

A foam with the following mechanical properties is obtained Characteristics:

Density according to DIN 53 420 (kg / m ³ ) 35 Tensile strength according to DIN 53 571 (kp / cm) 0.6 Elongation at break according to DIN 53 571 (%) 150 Compression test according to DIN 53 577 (p / cm ² ) 23 Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 0.6 Mean time to extinguish (sec.) 50.0 judgement self- going out

³⁵

40

Example 12

100 parts by weight of a started on Dioxydiphenylmethan polypropylene glycol, with ethylene oxide was modified so that at the end approx. 60% primary OH groups resulted with an OH number of 28,

3.5 parts by weight of water

0.1 part by weight of endoethylene piperazine

0.6 parts by weight of triethylamine

1.2 parts by weight of alkyl / phenyl siloxane 1

are mixed with one another and treated with 45.5 parts by weight of a polyisocyanate containing biuret groups, which by reacting a mixture of 2,4- and 2,6-tolylene diisocyanate with an isomer ratio of 80: 20 percent by weight and water has been produced (NCO content 38.5%), for Brought reaction. A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 35

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.7

Elongation at break according to DIN 53 571 (%) 160

Compression test according to DIN 53 577 (p / cm ² ) 23
Flammability according to
ASTM D 1692-67 T

30 5.7 47.0 self-extinguishing

4 Burning distance / mean value (cm) Mean extinguishing time (sec.)
judgement

Example 13

100 parts by weight of a started on trimethylolpropane polypropylenetriol, the so with ethylene oxide was modified so that at the end approx. 60% primary hydroxyl groups resulted with an OH number of 20,

3.5 parts by weight of water
0.1 part by weight of endoethylene piperazine 5.0 parts by weight of trichlorethylene phosphate 1.0 part by weight of alkyl / phenyl siloxane 1

are mixed with one another and treated with 43.0 parts by weight of a polyisocyanate containing biuret groups, which has been produced by reacting 2,4-tolylene diisocyanate and water (NCO content 38.5%), caused to react.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 37

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.6

Elongation at break according to DIN 53 571 (%) 140

Compression test according to DIN 53 577 (p / cm ² ) 23 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 3.0

Average extinguishing time (sec.) 25.0

Self-extinguishing assessment

Example 14

100 parts by weight of a started on trimethylpropane polypropylenetriol, the so with ethylene oxide was modified so that at the end approx. 70% primary hydroxyl groups with an OH number of 32 resulted

2.5 parts by weight of water
0.1 part by weight of endoethylene piperazine 1.0 part by weight of Ν, Ν-dimethylbenzylamine 2.5 parts by weight of alkyl / phenyl siloxane 1

are mixed with one another and treated with 38.0 parts by weight of a polyisocyanate containing biuret groups, which is obtained by reacting a mixture of 2,4- and 2,6-tolylene diisocyanate, (isomer ratio 65: 35 percent by weight) and water has been prepared (NCO content 38.5%), reacted.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 40

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.7

Elongation at break according to DIN 53 571 (%) 130

Compression test according to DIN 53 577 (p / cm ² ) 25 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 7.0

Average extinguishing time (sec.) 60.0

Assessment self-

veriöscheiiu

At game 15

100 parts by weight of a started from trimethylolpropane polypropylenetriol, the so with ethylene oxide

was modified so that at the end approx. 60% primary hydroxyl groups resulted with an OH number of 48,

2.5 parts by weight of water
0.1 part by weight of endoethylene piperazine 0.3 part by weight of N, N-dimethylbenzylamine 0.2 part by weight of alkyl / phenyl-siloxane 1

are mixed with one another and treated with 38.0 parts by weight of a polyisocyanate containing biuret groups, which is obtained by reacting a mixture of 2,4- and 2,6-tolylene diisocyanate (isomer ratio 80: 20 percent by weight) and water has been produced (NCO content 38.5%, reacted.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 42

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.7

Elongation at break according to DIN 53 571 (%) 120

Compression test according to DIN 53 577 (p / cm ² ) 25 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 6.0

Average time to extinguish (sec.) 35

Self-extinguishing assessment

Example 16

JO

100 parts by weight of a glycerine-started polypropylene triol that is modified with ethylene oxide it was found that at the end 28% primary hydroxyl groups result with an OH number of 56,

^{2.5 parts by} weight of water 3j

0.20 part by weight of endoäthylanpiperazine 0.1 part by weight of pentamethyl diethylenetriamine 1.0 part by weight of alkyl / phenyl siloxane 1

are mixed together and treated with 42.0 parts by weight of a polyisocyanal containing biuret groups, which is obtained by reacting a mixture of 2,4- and 2,6-tolylene diisocyanate (isomer ratio 65: 35 percent by weight) and water has been prepared (NCO content 38.5%), reacted. 4th

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 45

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.7

Elongation at break according to DIN 53 571 (%) 120

Compression test according to DIN 53 577 (p / cm ² ) 30 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 4.0

Average time to extinguish (sec) 38

Self-extinguishing assessment

Example 17

b0

100 parts by weight of a glycerine-based polypropylene alcohol modified with ethylene oxide it was found that at the end 60% primary hydroxyl groups resulted with an OH number of 35,

2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine 0.5 part by weight of tetramethylethylene diamine 1.2 parts by weight of alkyl / phenyl siloxane 3

are mixed with one another and treated with 38.0 parts by weight of a polyisocyanate containing biuret groups, which is obtained by reacting a mixture of 2,4- and 2,6-tolylene diisocyanate (isomer ratio 80: 20 percent by weight) and water has been prepared (NCO content 38.5%), reacted.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 40

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.7

Elongation at break according to DIN 53 571 (%) 130

Compression test according to DIN 53 577 (p / cm ² ) 30 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 5.5

Average reset time (sec.) 42

Self-extinguishing assessment

Example 18

100 parts by weight of a glycerine-started polypropylene triol that is modified with ethylene oxide It was found that about 60% primary hydroxyl groups with an OH number of 48 resulted at the end.

2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine 1.0 part by weight of triethylamine 1.5 parts by weight 1,4-butanediol 1.0 parts by weight alkyl / phenyl-siloxane 1

with 40.5 parts by weight of a biuret group containing polyisocyanate, which is obtained by reacting a mixture of 2,4- and 2,6-tolylene diisocyanate (Isomer ratio 80: 20 percent by weight) and water has been produced (NCO content 38.5%), brought to reaction.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 48

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.9

Elongation at break according to DIN 53 571 (%) 130

Compression test according to DIN 53 577 (p / cm ² ) 28 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 3.5

Average time to extinguish (sec.) 35

Assessment self-

going out

Example 19

100 parts by weight of a dipropylene glycol started polypropylene glycol, the so with ethylene oxide was modified so that at the end approx. 60% primary hydroxyl groups with an OH number of 28 resulted.

2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine, 0.5 part by weight of tetramethylethylene diamine 1.5 parts by weight tripylene glycol 2.0 parts by weight alkyl / phenyl-siloxane 2

are with 41.5 parts by weight of a polyisocyanate containing biuret groups, which by reaction

tion of a mixture of 2,4- and 2,6-tolylene diisocyanate (Isomer ratio 80: 20 percent by weight) and water has been produced (NCO content 38.5%) brought to reaction.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 45 Tensile strength according to DIN 53 571 (kp / cm ² ) 0.8 Elongation at break according to DIN 53 571 (%) 120 Compression test according to DIN 53 577 (p / cm ² ) 30th Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 3.7 Mean time to extinguish (sec.) 28 judgement self going out

20th

20th

25th

example

100 parts by weight of a started on trimethylolpropane polypropylenetriol, the so with ethylene oxide was modified so that at the end approx. 75% primary hydroxyl groups resulted with an OH number of,

2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine

1.5 parts by weight of N, N-dimethylbenzylamine

1.0 part by weight diethylene glycol

1.5 parts by weight of alkyl / phenyl siloxane 1

with 41.5 parts by weight of a polyisocyanate containing biuret groups, which is obtained by reaction of 2,4-tolylene diisocyanate and water (NCO content 38.5%), for the reaction brought.

A foam with the following mechanical properties is obtained Characteristics:

40

Density according to DIN 53 420 (kg / m ³ ) Example 21 45 Tensile strength according to DIN 53 571 (kp / cm ² ) 0.9 Elongation at break according to DIN 53 571 (%) 130 Compression test according to DIN 53 577 (p / cm ² ) 32 Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 3.5 Mean time to extinguish (sec.) 30.0 judgement self going out

100 parts by weight of a glycerine-started polypropylene triol that is modified with ethylene oxide it was found that at the end approx. 65% primary hydroxyl groups resulted with an OH number of 30,

2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine

0.8 part by weight of 1,4-butanediol

0.2 part by weight of tetramethylethylenediamine

1.8 parts by weight of alkyl / phenyl siloxane 1

with 40.5 parts by weight of a polyisocyanate containing biuret groups, which is obtained by reaction of 2,4-tolylene diisocyanate and water (NCO content 38.5%), for the reaction brought.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 46

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.7

Elongation at break according to DIN 53 571 (%) 120

Compression test according to DIN 53 577 (p / cm ² ) 30 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 4.2

Average time to extinguish (sec.) 30

Assessment self-

going out

Example 22

100 parts by weight of a started on trimethylolpropane Polypropylenetriol, which has been modified with ethylene oxide so that the terminal ends are about 60% primary Hydroxyl groups with an OH number of 35 resulted,

3.0 parts by weight of water

0.2 part by weight of endoethylene piperazine 1.0 part by weight of triethylamine 1.0 part by weight of alkyl / phenyl siloxane 1

with 48.5 parts by weight of a polyisocyanate containing biuret groups, which is obtained by reaction a mixture of 4,4'- and 2,4'-diphenylmei'häuoiisö-cyaHa *, · ■ IsoTOer.e.nv.er.h.ältnis ^ 60: 40 percent by weight, and water has been produced (NCO content 30.0%), reacted.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 42 Tensile strength according to DIN 53 571 (kp / cm ² ) 1.0 - Elongation at break according to DIN 53 571 (%) 140 Compression test according to DIN 53 577 (kp / cm ² ) 38 Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 5.3 Mean time to extinguish (sec.) 40 judgement self going out

50

Example 23

100.0 parts by weight of a polypropylene triol started on hexanetriol and modified with ethylene oxide it was found that at the end approx. 60% primary hydroxyl groups resulted with an OH number of 35.0,

2.5 parts by weight of water
0.1 part by weight of endoethylene piperazine 0.7 part by weight of N-ethylmorpholine 0.20 part by weight of alkyl / phenyl-siloxane 1

are mixed together and with 38.0 parts by weight of isocyanate adduct (NCO content 35%), from trimethylpropane and 2,4- and 2,6-tolylene diisocyanate (isomer ratio 80: 20 percent by weight) produced, reacted.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 43

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.7

Elongation at break according to DIN 53 571 (%) 130

Compression test according to DIN 53 577 (p / cm ² ) 25 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 3.5

Mean time to extinguish (sec.)
judgement

28

self-extinguishing

Example 24

100.0 parts by weight of a glycerine-started polypropylene triol which is modified with ethylene oxide in this way it was found that at the end approx. 60% primary hydroxyl groups result with an OH number of 35.0,

2.5 parts by weight of water
0.18 part by weight of endoethylene piperazine
0.5 part by weight of tetramethylethylenediamine
3.0 parts by weight of alkyl / phenyl siloxane 1

are mixed together and with 38.0 parts by weight of isocyanate adduct (NCO content 35%), from trimethylpropane and 2,4- and 2,6-tolylene diisocyanate (isomer ratio 80: 20 percent by weight) and reacted.

A foam with the following mechanical properties is obtained:

Density DIN 53 420 (kg / m ³ ) 44 Tensile strength according to DIN 53 571 (kp / cm ² ) 0.6 Elongation at break according to DIN 53 571 (%) 120 Compression test according to DIN 53 577 (p / cm ² ) 25th Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 4.0 Mean time to extinguish (sec.) 35 judgement self going out

Example 25

100.0 parts by weight of a trimethylolpropane started polypropylenetriol, the so with ethylene oxide was modified so that at the end approx. 70% primary hydroxyl groups resulted with an OH number of 32.0,

2.5 parts by weight of water
0.15 part by weight of endoethylene piperazine
1.0 part by weight of N, N-dimethylbenzylamine
1.3 parts by weight of alkyl / phenyl siloxane 3

are mixed together and with 35.0 parts by weight of isocyanate adduct (NCO content 35%), from trimethylpropane and 2,4- and 2,6-tolylene diisocyanate (isomer ratio 80:20 percent by weight), brought to reaction.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ^J ) 44

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.7

Elongation at break according to DIN 53 571 (%) 135

Compression test according to DIN 53 577 (p / cm ² ) 28
Flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 4.5

Average time to extinguish (sec.) 35

Self-assessment

extinguishing

Example 26

100.0 Gcwichtstcilc of a propylene glycol started from propylene glycol, which with ethylene oxide so was modified so that about 60% primary at the end

Γ)

Hydroxyl groups with an OH number of 28 resulted,

3.5 parts by weight of water
0.1 parts by weight of endoethylene piperazine 3.25 parts by weight of diisopropanolamine 0.80 parts by weight of alkyl / phenyl-siloxane 1

are mixed with one another and with 55.60 parts by weight of isocyanate adduct (NCO content 35%), from trimethylpropane and 2,4- and 2,6-tolylene diisocyanate (isomer ratio 80:20 percent by weight) prepared for Brought reaction.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 39 Tensile strength according to DIN 53 571 (kp / cm ² ) 1.1 Elongation at break according to DIN 53 571 (%) 140 Compression test according to DIN 53 577 (p / cm ² ) 30th Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 5.7 Mean time to extinguish (sec.) 50 judgement self going out

Example 27

100.0 parts by weight of a glycerine-started polypropylene triol which is modified in this way with ethylene oxide it was found that at the end approx. 70% primary hydroxyl groups resulted with an OH number of 32,

2.5 parts by weight of water

0.2 part by weight of endoethylene piperazine 1.0 part by weight of Ν, Ν-dimethylbenzylamine 1.5 parts by weight of diethylene glycol 3.0 parts by weight of monofluorotrichloromethane · 1.2 parts by weight of alkyl / phenyl-siloxane 1

are with 37.5 parts by weight of isocyanate adduct (NCO content 35%), from trimethylolpropane and 2,4- and 2,6-toluylene diisocyanate (isomer ratio 80:20 Ge weight percent) produced, brought to reaction.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 43 Tensile strength according to DIN 53 571 (kp / cm ² ) 0.6 Elongation at break according to DIN 53 571 (%) 135 Compression test according to DIN 53 577 (p / cm ² ) 35 Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 3.0 Mean time to extinguish (sec.) 30th judgement self going out

Example 28

A) 100.0 parts by weight of a polypropylene triol started on Hcxantriol, the so modil with ethylene oxide it was adorned that at the end approx. 60% primary hydroxyl groups resulted with an OH number of 35.0,

2.5 parts by weight of water
0.15 part by weight of endoethylene pipcrazine 0.7 part by weight of N-ethylmorpholine 1.0 part by weight of alkyl / phenyl-siloxane 3

are mixed together and 40.0 parts by weight of an allophanate polyisocyanate (NCO-Geh 35.1%) reacted.

7Ü9 M5 /

B) Preparation of the polyisocyanate

134 parts of trimethylolpropane are in the course of about 1 hour to submitted, at 80 ⁰ C heated tolylene 2,4- and 2,6-diisocyanate: added to give the reaction mixture to 114 ° C heated (isomer ratio 80 20). After reaching a content of 41.3% NCO immediately after the end of the trimethylolpropane addition, the mixture is heated to 150 ° C. and left at this temperature for 20 hours. The result is a solution of an allophanate polyisocyanate in a mixture of toluene diisocyanate isomers with an NCO content of 38.1% and a viscosity of 77 cP ₂₅ * c

To 1900 parts of this solution, 100 parts of 2,3-dibromopropanol-l was added and reacted for 2 V ₂ hours at 90 ⁰ C at 8O ⁰ C. The modified allophanate polyisocyanate in toluylene diisocyanate isomer mixture is characterized by an NCO content of 35.1%, a viscosity of 118 CP25-C and a solids content of 41%. :O

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 50

Tensile strength according to DIN 53 571 (kp / cm ² ) 0.8

Elongation at break according to DIN 53 571 (%) 120

Compression test according to DIN 53 577 (p / cm ² ) 35
Flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 3.0

Average time to extinguish (sec.) 25

Self-extinguishing assessment

Example 29

A) 100.0 parts by weight of one started on glycerol Polypropylenetriol, which has been modified with ethylene oxide so that 60% primary hydroxyl groups at the end resulted in an OH number of 35.0,

2.5 parts by weight of water
0.1 part by weight of endoethylene piperazine
0.5 part by weight of tetramethylethylenediamine
1.0 part by weight of alkyl / phenyl siloxane 2

are mixed with one another and "with 40.0 parts by weight of an allophanate polyisocyanate (NCO content 35.1%) reacted.

B) Preparation of the polyisocyanate

134 parts Trimethylolpropari be over a period of about I hour to submitted, heated to 8O ⁰ C tolylene 2,4- and 2,6-diisocyanate (Isonierenverhältnis 80: 20) was added, and the reaction mixture heated to 114 C. After reaching a content of 41.3% NCO immediately after the end of the trimethylolpropane addition, the mixture is heated to 150 ° C. and left at this temperature for 20 hours. The result is a solution of an allophanate polyisocyanate in a mixture of toluene diisocyanate isomers with an NCO content of 38.1% and a viscosity of 77 cPjvi ·.

To 1900 parts of this solution at 80 "C, 100 parts of 2,3-dibromopropanol-l added, and for 2 '/ 2 hours at 9O ⁰ C reacted, The modified allophanate-polyisocyanate inToluylendiisocyanat isomer mixture is characterized by a content of 35 , 1% NCO, a viscosity of 118 cP ₂₅ c and solids content of 41%.

A foam with the following mechanical properties is obtained Characteristics:

Density according to DIN 53420 (kg / m ³ ) 50

Tensile strength according to DIN 53571 (kp / cm ² ) 0.8

Elongation at break according to DIN 53571 (%) 130

Compression test according to DIN 53577 (p / cm ² ) 30 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 3.6

Average time to extinguish (sec.) 28

Self-extinguishing assessment Example 30

A) 100.0 parts by weight of a trimethylolpropane started polypropylenetriol, the so with ethylene oxide was modified so that at the end approx. 60% primary hydroxyl groups resulted with an OH number of 35,

2.5 parts by weight of water
0.2 part by weight of endoethylene piperazine 1.0 part by weight of dimethylbenzylamine 1.0 part by weight of alkyl / phenyl-siloxane 1

are mixed together and with 38.0 parts by weight of an allophanate polyisocyanate (NCO content 35.1%) reacted.

B) Preparation of the polyisocyanate

134 parts of trimethylolpropane are in the course of about 1 hour to jo submitted, heated to 8O ⁰ C tolylene 2,4- and 2,6-diisocyanate (isomer ratio 80: 20) was added, and the reaction mixture heated to 114 C. After reaching a content of 41.3% NCO immediately after the end of the trimethylolpropane addition, the mixture is heated to 150 ° C. and left at this temperature for 20 hours. The result is a solution of an allophanate polyisocyanate in a mixture of toluene diisocyanate isomers with an NCO content of 38.1% and a viscosity of 77 cP ₂ 5 »c. A foam with the following mechanical properties is obtained:

Density according to DIN 53420 (kg / m ³ ) 48

Tensile strength according to DIN 53571 (kp / cm ² ) 0.8

Elongation at break according to DIN 53571 (%) 120

Compression test according to DIN 53577 (p / cm ² ) 35 flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 4.0

, ο Average extinguishing time (sec.) 42

Assessment self-

going out

Example 31

A) 100.0 parts by weight of a dipropylene glycol started polypropylene glycol with ethylene oxide was modified so that at the end 60% primary hydroxyl groups resulted with an OH number of 28.0,

2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine

0.4 parts by weight of N-ethylmorpholine

0.4 parts by weight of triethylamine 1.3 parts by weight of alkyl / phenyl-siloxane 1

are mixed with each other and with 37.0 Wcwichtstcilen an allophanate polyisocyanate (NCO content 35.1%) reacted.

B) Preparation of the polyisocyanate

134 parts of trimethylolpropane are in the course of about 1 hour to submitted, at 80 ⁰ C heated tolylene 2,4- and 2,6-diisocyanate: added to give the reaction mixture to 114 ° C heated (isomer ratio 80 20). After reaching a content of 41.3% NCO immediately after the end of the trimethylolpropane addition, the mixture is heated to 150 ° C. and left at this temperature for 20 hours. The result is a solution of a ιυ allophanate-polyisocyanate in toluylene diisocyanate isomer mixture with a content of 38.1% NCO and a viscosity of 77 cP ₂ 5 ° o

To 1900 parts of this solution, 100 parts of 2,3-dibromopropanol-l was added and reacted for 2 '/ 2 hours at 90 ⁰ C at 8O ⁰ C. The modified allophanate polyisocyanate in toluene diisocyanate isomer mixture is characterized by an NCO content of 35.1%, a viscosity of 118 cP25 ° C and a solids content of 41%.

A foam with the following mechanical properties is obtained:

Density according to DIN 53420 (kg / m ³ ) 42 Tensile strength according to DIN 53571 (kp / cm ² ) 0.7 Elongation at break according to DIN 53571 (%) 130 Compression test according to DIN 53577 (p / cm ² ) 30th Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 4.4 Mean time to extinguish (sec.) 30th judgement self going out

Example 32

100 parts by weight of a started on trimethylolpropane polypropylenetriol, the so with ethylene oxide was modified so that at the end approx. 60% primary hydroxyl groups resulted with an OH number of 35.

3.0 parts by weight of water
0.2 part by weight of endoethylene piperazine
0.2 part by weight of tetramethylethylenediamine
5.0 parts by weight of trichloroethyl phosphate
1.0 part by weight of alkyl / phenyl siloxane 1

are mixed together and 40.5 parts by weight of a mixture consisting of 60 parts by weight of 2.4 and 2,6-tolylene diisocyanate (isomer ratio 65:35) and 40 parts by weight of a polyphenyl polymethylene polyisocyanate (NCO content 31%) brought to reaction.

A foam with the following mechanical properties is obtained Characteristics:

Density according to DIN 53420 (kg / m ^J ) 35

Tensile test according to DIN 53571 (kp / cm ² ) 0.5

Elongation at break according to DIN 53571 (%) 90

Compression test according to DIN 53577 (p / cm ² ) 18

Flammability according to

ASTM D 1692-67 T
Burning distance / mean value (cm)
Mean time to extinguish (sec.)
judgement

jo

35

45

v-, 4.9
35

self-extinguishing

33

example

A) 100 parts by weight of a glycerine-started polypropylene triol that is modified with ethylene oxide It was found that 80% of primary hydroxyl groups at the end with an OH number of 31 resulted, 5 parts by weight of a polyester with an OH number of 370, produced from adipic acid, phthalic anhydride and trimethylpropane.

3.2 parts by weight of water

0.15 part by weight diazabicyclo-2,2,2-octane

0.4 parts by weight of triethylamine

1.0 part by weight of the alkyl / phenyl siloxane 1

are mixed together and with 50.1 parts by weight the subsequently described polyisocyanate reacted in a closed form.

B) Preparation of the polyisocyanate

To a mixture of 225 parts by weight of a mixture of 80 percent by weight of 2.4 and 20 percent by weight of 2,6-tolylene diisocyanate and 274 parts by weight of 4,4'-diphenylmethane diisocyanate, 20 parts by weight of 1,2-propylene glycol are added ^{at 60 ° C. and added for 30 minutes} Implementation brought. After addition of 1 part by weight of / 3-Phenyläthyläthylenimin is heated to 130 ⁰ C. Which takes place at this temperature trimerization is stopped by adding 1 part by weight of p-toluenesulfonic acid methyl ester by 2 'Ii hours at an NCO content of the reaction mixture of 26.5%.

After dilution with 624 parts by weight of a mixture of 2,4- and 2,6-tolylene diisocyanate (80.20 Percent by weight) a polyisocyanate solution is obtained, which by an NCO content of 38.4%, is marked.

A foam with the following mechanical properties is obtained:

Density according to DIN 53420 (kg / m ^J ) 46 Tensile test according to DIN 53571 (kp / cm ² ) 1.25 Elongation at break according to DIN 53571 (%) 100 Compression test according to DIN 53577 (p / cm ² ) 63 Flammability according to ASTM D 1692-67 T Burning distance / middle! V / ert (cm) 4.0 Mean time to extinguish (sec.) 39 judgement self- going out

Claims (1)

Patent claims: 1. Process for the production of flame-retardant, non-shrinking, open-pored, urethane groups exhibiting foams made of polyethers containing active hydrogen atoms with a Molecular weight from 750 to 10,000, optionally mixed with low molecular weight compounds with active hydrogen atoms and a molecular weight of up to 750 or up to 50 percent by weight, based on the polyether, with higher molecular weight polyesters, polyacetals, polyester amides and polycarbonates, polyisocyanates, water and / or organic blowing agents in the presence of alkyl / phenyl siloxanes in amounts from 0.1 to 25% by weight and optionally in the presence of catalysts, characterized in that that as alkyl / phenyl siloxanes a mixture of Compounds of the general formula