DE2232525C3 - Process for the production of flame-retardant, non-shrinking, open-pored foams containing urethane groups - Google Patents

Description

Group and at least one isocyanuric acid ring-containing polyisocyanate in isocyanurate group-free Polyisocyanates in question.

High flame resistance in the case of urethane groups Foam means that they are self-extinguishing according to ASTM method D 1692 - 67 T 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 commercial 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.

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 ₃ SiO

R '

Si-04-SiR ₃

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, polyurethanes, including foamed polyurethanes, are produced by reacting any polyisocyanates with any hydroxy compounds, such as polyesters and polyethers, in the presence of conventional methyl / phenyl polysiloxanes. The methyl / Phe-H) nyl-polysiloxanes used should have an improved solubility in the reaction mixture - compared to dimethylpolysiloxanes. 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, undesired bubble formation in the interior of foams and under the foam surface can be prevented. The object and purpose of the present invention are therefore absolutely different from the object on which the British patent specification Jag is based. This patent specification therefore gives no information on how to prevent undesirable bubble formation in the interior of foams and under the foam surface during foam production. 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

Γι reaction mixture and the nucleation of the Foaming process is greatly favored, which in the case of the production of foams by shaping with long flow paths or strongly changing cross-sections, the advance

4 (i represents the setting for optimal production, and that the stability of the reaction mixture is improved and after the foaming process a fine formed cell structure is obtained, up to the foam surface in the case of production of foams through shaping.

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

> () 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 built-in graze and spread evenly throughout the entire mass.

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

do 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 lead to foams with the assessment "flammable" according to ASTM D 1692 - 67 T.

for the implementation of the method according to the invention, the known aÜDhatischen come.

cycloaliphatic, araliphatic and aromatic Polyisocyanates into consideration, for example

1 ^ tetramethylene diisocyanate.

1,6-hexamethylene diisocyanate.

l. ^ - dodecane diisocyanate,

Cyclohexane 1,3- and 1,4-diisocyanate

as well as any mixtures of these isomers,

l-isocyanato-S.S.S-trimethyl-S-isocyanato-

methyl-cyclohexane,

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

2,4- and 2,6-tolylene diisocyanate

as well as any mixtures of these isomers,
2,4- and 2,6-He cahydrotoluylene diisocyanate
as well as any mixtures of these isomers,
Diphenylmethane-4,4'-diisocyanate,
Naphthylene-1,5-diisocyanate,
Triphenylmethane-4,4 ', 4 "-triisocyanate,
Polyphenyl-polymethylene-polyisocyanate,
as they are obtained by aniline-formaldehyde Koi.densation and subsequent phosgenation, carbodiimide isocyanate adducts containing polyisocyanates as obtained according to DT-PS 10 92 007, diisocyanates as described in US-PS 34 92 330, Polyisocyanates containing allophanate groups, as described in GB-PS 9 94 890, BE-PS 7 61 626 and ·. published Dutch patent application 71 02 524, is> icyanuratgruppen containing polyisocyanates, as described in DE-PSs 10 22 789 and 10 27 394 and in DE-OSs 19 29 034 and 20 04 048. Polyisocyanates containing biuret groups, as described in DE-PS 11 01 394, GB-PS 8 89 050 and FR-PS 70 17 514, polyisocyanates produced by telomerization reactions, as described in BE-PS 7 23 640 are described, polyisocyanates containing ester groups according to the GB-PSs

9 56 474 and 10 72 956. also aliphatic, cycloaliphatic, araliphatic or aromatic polyisocyanates, as described by W. S i e f g e η in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, are mentioned, reaction products the above-mentioned polyisocyanates with acetals according to DE-PS 10 72 385 and polyisocyanates, as described in DE-PSs 10 22 789 and

10 27 394 can be mentioned.

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

The technically easily accessible polyisocyanates, for example that, are generally particularly preferred 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", d. H. 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". As "unmodified polyisocyanates" come mainly toluene-2,4- and / or 2,6-diisocyanate, optionally mixed with 4,4'-diphenyl methylene diisocyanate, in a carrier.

The preparation of the allophanate polyisocyanates can, for. B. be carried out according to BE-PS 7 63 329, wherein Diisocyanates such as toluene-2,4-diisocyanate or mixtures thereof with toluene-2,6-diisocyanate are preferred be used. Their solutions generally have a content of 5 to 85% by weight, preferably 10 up to 50% by weight of allophanate polyisocyanate.

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

Ii

OCN-R-N-C "N-R-NCO

OCN-R-N-C = O X

in which R is a C1 to C1 alkylene radical, Cs- to CnrCycloalkylenrest, C-- to C ^ -aralkylenrest or C ,, to Cio-Arylenrtst and X hydrogen or the grouping

X = - (CO- NI _n - H

R - NCO

means in which R has the meaning already mentioned and π is an integer from 0 to 5, in biuret-free polyisocyanates, the proportion of biuret polyisocyanates with more than 3 isocyanate groups, based on the total amount of polybiuret isocyanates, at least 20% by weight o is. The preparation of polyisocyanates containing biuret groups is described, for example, in GB-PS 8 89 050 and in DTPS 11 01 394. 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. DE-OS 19 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 from uranium groups.

Solutions of at least one isocyanuric acid ring-containing polyisocyanate in liquid polyisocyanates free from isocyanurate groups are also used as "modified polyisocyanates". Such Unr'Kaniiratirriinnfn QiifwpknnHi ¹ Pnlv / i * u> rv: in: (to spwir

Process for their preparation are /. H. in DE-PS'en9 51 168 and 10 22 789, in GB-PS 8 21 158, 8 27 120.8 56 372.4 27 173.9 20 080 and «52 931, in U.S. Patents 3,154,522, 2,801,244, in I R-PS 1,510,342 as well as BE-PS 7 18 994 besehrieben. As polyisocyanates that contain at least one isocyanuric acid ring have, the polymers preferably come from 2,4- or 2,6-tolylene diisocyanate or any Mixtures of these isomers, optionally mixed with 4,4'-diphynylmethane diisocyanate in question. The solutions are obtained by having 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-1,5-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 won. Polyphenyl polymethylene 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, 1,10-decanediol, butyn-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-naphthol, 2 ^ -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, aminoethylpiperazine, 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. The adducts of 1,2-alkylene oxides with ethanolamine, Diethanolamine, methyldiethanolamine, triethanolamine and ammonia are suitable. As start media Resin-like materials of the phenol and resol type also come into consideration.

All of these polyethers are preferably constructed using ethylene oxide. The mentioned Polyethers can also be modified by reacting less than equivalent amounts of polyisocyanate will.

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 wt .-%, 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 Compounds with active hydrogen atoms or on 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. This is advantageously used machine facilities such. B. in FR-PS 1047 713 are described.

The following should be mentioned as emulsifiers and additives:

Suitable emulsifiers are, for. B. ethylene oxide or ethylene oxide / propylene oxide adducts to hydrophobic Substances containing hydroxyl or amino groups or amido groups.

As catalysts for the production of the foams, for. B. tertiary amines and / or silaamines, N-substituted aziridines and hexahydrotriazines are used, optionally in combination with organic ones Metal connections. While the amines preferentially catalyze the Trejb reaction, the organic ones act Metal compounds preferentially on the crosslinking reaction. To achieve foaming technology Favorable reaction times will depend on the particular constitution of the chosen catalyst or the catalyst mixture, the amount of catalyst to be used is determined empirically. As amines such compounds, which are well known for the production of polyurethane foams, can be used be, for example

Dimethylbenzylamine, N-methylmorpholine,
Triethylenediamine, dimethylpiperazine,
1,2-dimethylimidazole, dimethylethanolamine,
Diethanolamine, triethanolamine,
Diethylaminoethanol,
Tetramethyl-13-butanediamine,

N-methyl-N'-dimethyl-aminoethyl-piperaz.in and
Pentamethylene triamine.

Silaamines are silicon compounds that contain carbon-silicon bonds, such as they are described, for example, in DE-PS 12 29 290. Examples are 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 i < > Sodium methylate, suitable. The optionally in combination with amines, silaamines and those from the Organic metal compounds used in DE-OS 17 69 043 known hexahydrotriazines are preferred organic tin compounds, e.g. B. Tin (!!) octate or dibutyltin dilaurate.

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

Preferably, the foaming is done in forms _ό carried out. The reaction mixture is introduced into a mold. Metal is used as the molding material, z. B. aluminum or plastic, e.g. B. epoxy resin in question. The foamable foams in the mold Reaction mixture and forms the shaped body. The 2> foam molding can be carried out in such a way that 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, you can proceed that so much foamable reaction mixture is introduced into the mold that the foam formed just fills the shape. But you can also work in such a way that you get more foamable reaction mixture enters the mold than is necessary to fill the inside of the mold with foam. One such procedure is z. B. from US-PS 11 78 490 or 31 82 104 known.

In the case of foam molding, release agents known per se are often also used.

Cold-curing foams, in particular, are produced by the process according to the invention (see GB-PS 11 62 517 and DE-OS 21 53 086).

The alkyl / phenyl siloxanes used in the process according to the invention are known and can 4-, z. B. be prepared by the process of DE-PS 10 46 049 or US-PS 30 12 052.

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

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 Phenyl radical means 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 = 1 «ι

14.5 parts by weight of a compound of the general Formula with the value a = 2

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

Alkyl / phenyl siloxane 2 ^b5

15.0 parts by weight of a compound of the general formula with the value a = 0

71.0 parts by weight of a compound of the general

Formula with the value a = I
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

At 60 ° C., 20 parts of 1,2-propylene glycol are added to a mixture of 225 parts of a mixture of 80% by weight of 2,4- and 20% by weight of 2,6-tolylene diisocyanate and 274 parts of 4,4'-diphenylmethane diisocyanate added and brought to reaction for 30 minutes. After the addition of 1 part of j3-Phenyläthyläthylenamin is heated to 130 ⁰ C. The trimerization which takes 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-toluene diisocyanate, a polyisocyanate solution is obtained which, by the values NCO content (%): 38.4, viscosity cP ₂ 5c: 24, refractive index ηi °: 1.5738 is marked.

B) Manufacture of the foam

100 parts by weight of one started on dipropylene glycol Polypropylene glycol, which has been modified with ethylene oxide so that 60% primary at the end Hydroxyl groups with an OH number of 28 resulted,

3.5 parts by weight of water

0.1 part by weight of endoethylene piperazine

0.4 parts by weight of triethylamine

0.9 parts by weight of the alkyl / phenyl siloxane 1

are mixed together and mixed 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 / mJ) 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 ) 25
Flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 6.0

Average time to extinguish (sec.) 35

Assessment self-

extinguishing

Example! 2
A) Preparation of the polyisocyanate

To 273 parts of the mixture mentioned in Example 1 of 2,4- and 2,6-tolylene diisocyanate at 6O ⁰ C and 133 parts of 1,2-propylene glycol, and after 30 minutes of reaction time during which the approach at 8O ⁰ C

heated, treated with 0.044 parts / i-phenylethylethyleneimine. Under nitrogen as protective gas is now heated to 130 ⁰ C, and the trimerization after about 5 hours reaction time at that temperature by the addition of 0.042 parts of benzoyl chloride at a - stopped> NCO value of 25.8%. After the reaction mixture has been diluted with 71.50 parts of a 65/35 mixture of 2,4- and 2,6-toluylene diisocyanate, 5.28 parts of 2,3-dibromopropanol are added to this solution and the mixture is added at 80 to 90 ^° C. for 2 hours Dictionary n> brought. The modified polyisocyanate solution is characterized by the values of NCO content (%): 38.5, viscosity cP? V <: 26 and refractive index n ^s _D °: 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 resulted with an OH number of 28, - '< >

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

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 / mJ) Example 3 40 π Tensile test 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 ) 25th Flammability according to ASTM D 1692-67 T 4 (1 Burning distance / mean value (cm) 3.5 Mean time to extinguish (sec.) 25th judgement self going out

A) Preparation of the polyisocyanate

4 y

To 25.0 parts of the mixture of 2,4- and 2,6-tolylene diisocyanate mentioned in Example 1, 0.040 parts of a solution of water in acetone (25 g of water, made up to 1000 ml with acetone) and 0.038 parts are added at 22.degree / 9-Phenylethylethyleneimine added. After a short incubation time, the slightly exothermic trimerization of the diirrocyanate begins, which occurs after a reaction time of approx. 2 to 2 1/2 hours at an NCO content of 31% and a reaction ^{temperature of now 70 °} C. by adding 0.024 parts - »p-Toluenesulfonic acid methyl ester is stopped. At a temperature of the reaction mixture of 80 ^° C., 3 parts of tripropylene glycol are added to it and the reaction mixture is reacted at the same temperature for ^{1 1/2 hours. B}

After addition of 75 parts of 80/20 mixture of 2,4- and 2,6-diisocyanate and intensive homogenization of the reaction components to the batch, 5.42 parts of 2,3-dibromopropanol at 90 ⁰ C added After 2 hours reaction time at 90 to bs 100 ⁰ C is the Polyisocyanatkombination characterized by NCO content (%): 38.2, viscosity CP ₂₅ - _c: 33 and refractive index n ^'y: 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 resulted with an OH number of 28,

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

Example 4
A) Preparation of the polyisocyanate

35.0 parts mentioned in Example 1 mixture of 2,4- and 2,6-tolylene diisocyanate are added at 6O ⁰ C and 1.96 parts of 1,2-propylene glycol and 30 minutes allowed to react, with the reaction mixture to 8O ⁰ C heated. After adding 0.037 parts /? - Phenyläthyläthylenimin is ^{heated to 130 0} C and left at this temperature, at which a trimerization of the isocyanate mixture takes place, until an NCO value of 30.0 is reached, which is about 1 to 2 Took hours of time. After cooling to 100 ° C., 3.70 parts of tripropylene glycol are added and the mixture is reacted at the same temperature over the course of 1 hour. The reaction mixture, characterized after this time by an NCO value of 23.3%, is now diluted with 65.06 parts of an 80/20 mixture of 2,4- and 2,6-tolylene diisocyanate. The polyisocyanate solution obtained has the following values: NCO content (%): 38.9, viscosity cP ₂ 5-c: 39, refractive index: / Jo ⁰ : 1.5642.

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. 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 of alkyl / phenyl siloxane 3

are mixed together and with 38.8 parts by weight of the polyisocyanate listed under A) reacted.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ¹ ) 41
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) 4.1

Average time to extinguish (sec.) 30

Self-extinguishing assessment

Example 5
A) Preparation of the polyisocyanate

The procedure is the same as described under 4 A), except that 2.03 parts of tripropylene glycol are used in proportions of trimethylolpropane 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 cP ₂ 5 c: 58, refractive index nif: 1.5682 is obtained.

B) Manufacture of the foam

100 parts by weight of a trimethylolpropane started polypropylenetriol. the one with ethylene oxide like that 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
0.1 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 mixed with 37.5 parts by weight of the polyisocyanate prepared under A) Brought reaction. A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / mJ) 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 ) 22
Flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 4.0

Average extinguishing time (sec.) 40.0

Self-extinguishing assessment
Example 6

A) Preparation of the polyisocyanate

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 / J-Phenyläthyläthylenimin is heated to 130 ⁰ 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 trimerization of the polyisocyanate is now stopped by adding 0.038 parts of methyl p-toluenesulfonate and, after cooling to 120 ° C., the mixture is diluted with 60.0 parts of an 80/20 mixture of 2,4- and 2,6-tolylene diisocyanate. The polyisocyanate is through the following values are identified: NCO content (%): 39.4, viscosity cP ₂ s (: 63, refractive index n?: 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 ι) reaction brought. A foam is obtained with the following mechanical properties:

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

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

jo elongation at break according to DIN 53 571 (%) 130

Compression test according to DIN 53 577 (p / cm- ¹ ) 22
Flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm) 4.0

Average time to extinguish (sec.) 45.0

Assessment self-

going out
Example 7

A) Preparation of the polyisocyanate

0.061 parts of a solution of water in acetone are added at 25 ° C. to 38.76 parts of toluene-2,4-diisocyanate (25 g of water, made up to 1000 ml with acetone) and 0.058 part of j2-phenylethyleneimine added. To

j-, short incubation period, the slightly exothermic begins Trimerization of the diisocyanate, which occurs after about 2 hours at an NCO value of 31.0 to 313% by addition stopped by 0.042 part of benzoyl chloride.

The reaction mixture is now brought to 80 ° C and 2.33 parts of tripropylene glycol in Over the course of 10 to 15 minutes, a reaction temperature of 95 to 100 ° C is reached. Without further supply of heat, the mixture is stirred for 1 hour and then with 58.91 parts of a mixture of 2.4

4- and 2,6-tolylene diisocyanate (80: 20% by weight) diluted. The solution of the modified isocyanurate polyisocyanate in toluene diisocyanate is characterized by the following values: NCO content (%): 39.5, viscosity cP ₂ 5 c 54, refractive index n ^? '-. \ , 5827.

B) Manufacture of the foam

100.0 parts by weight of a started on trimethylolpropane polypropylenetriol, the so with ethylene oxide was modified so that they resulted in 60% primary hydroxyl groups at the end with an OH number of 35.0,

2.5 parts by weight of water
0.1 parts by weight of endoethylene piperazine
0.8 parts by weight of triethyiamine
^h "2.0 parts by weight of alkyl / phenyl-siloxane 2

are mixed together and mixed with 373 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 ) 43

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

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

135
25th

4.0 42.0 self-extinguishing

Example 8 A) Preparation of the polyisocyanate

95 parts of the modified method described in Example 4 isocyanurate polyisocyanate in the toluene diisocyanate at 90 ⁰ C are added with 5 parts of 2,3-dibromopropanol and reacted for 2 hours at this temperature. The resulting polyisocyanate solution has the values NCO content (%): 36.0, viscosity cP ₂ 5c: 81, refractive index n ^? : Marked 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% great, e 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:

Density according to DIN 53 420 (kg / m ') 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'-Diphenylmeth & ndiisocyanat at 60 ⁰ C, 20 parts of 1,2-propylene glycol added and brought to reaction for 30 minutes. After adding 1 part / 3-phenylethylethyleneimine, the mixture is heated to 130.degree. 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 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 NCO content (%): 38.4, viscosity cPj, ₍ : 24, refractive index nl °: 1.5738 is marked.

B) Manufacture of the foam

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 of Ν, Ν-dimethylbenzylamine 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 ) Example 10 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 / NMtelwert (cm) 4.5 Mean time to extinguish (sec.) 42.0 judgement self going out

A) Preparation of the polyisocyanate

38.46 parts of toluene-2,4-diisocyanate are in one

1.54 parts of 1,2-propylene glycol are added under nitrogen as protective gas at 60 ^° C. and the reaction mixture is reacted for 30 minutes, the reaction mixture heating ^{to 95 to 100 ° C. without the supply of heat.} After adding 0.060 parts 0-Phenyläthyläthylenimin is heated to 130 ° C and at leave this temperature until an NCO value of 26.0% is reached after about 5 to 6 hours. the Trimerization of the polyisocyanate is now carried out by adding 0.038 parts of p-toluenesulfonic acid methyl

4> ester stopped and the mixture, after cooling to 12O ⁰ C and 60.0 parts of diluted 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 ₂ yc: 63, Brediungs-

w index: nf: 1.5721.

B) Manufacture of the foam

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

2.5 parts by weight of water ^h "0.20 parts by weight of endoethylene piperazine

0.3 parts by weight of N.N-dimethylbenzylamine 1.2 parts by weight of alkyl / phenyl siloxane 1

are mixed with one another and with 35.0 parts by weight of the polyisocyanate listed under A) Reaction brought.

A foam with the following mechanical properties is obtained:

809 626/189

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

11th

45

0.6
130
25th

5.0
30.0
self-extinguishing

J (I

Density according to DIN 53 420 (kg / m ³ ) 35 Tensile strength according to DIN 53 571 (kp / cm ² ) 0.6 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) 0.6 Mean time to extinguish (sec.) 50.0 judgement self going out

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 together and 45.5 parts by weight a polyisocyanate containing biuret groups, which is obtained 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 ¹ ) 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 Dl N 53 577 (p / cm ² ) 23
Flammability according to
ASTM D 1692-67 T

Burning distance / mean value (cm)
Mean time to extinguish (sec.)
judgement

13th

5.7
47.0
self-extinguishing

example

100 parts by weight of one started on dipropylene glycol Polypropylene glycol, which has been modified with ethylene oxide so that 60% primary at the end Hydroxyl groups with an OH number of 28 resulted,

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 mecha- j <is obtained > niche properties:

example

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 resulted in hydroxyl groups 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 by reaction of 2,4-tolylene diisocyanal 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 ) 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 ASTMD 1692-67 T Burning distance / mean value (cm) 3.0 Mean time to extinguish (sec.) 25.0 judgement self going out

Example 14

100 parts by weight of one started on trimethyl propane Polypropylenetriol, which has been modified with ethylene oxide so that the terminal ends are about 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 N, N-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 ) 25th Flammability according to ASTMD 1692-67 T Burning distance / mean value (cm) 7.0 Mean time to extinguish (sec.) 60.0 judgement .self going out

Example 15

100 parts by weight of a Polypropylcntriols started on trimethylolpropane, the so with ethylene oxide

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

2.5 parts by weight of water
0.1 part by weight of endoethylene piperazine 03 part by weight of N, N-dimethylbenzylamine 0.2 part by weight of alkyl / phenyl-siloxane 1

are mixed together and comprising 38.0 parts by weight of a biuret Polyisocya- w NATs obtained by reacting a mixture of 2,4- and 2,6-toluene diisocyanate: prepared (isomer ratio 80 20 weight percent) and water (NCO content 38 , 5%, reacted.

A foam with the following mechanism is obtained. niche properties:

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 _n

Compression test according to DIN 53 577 (p / cm ² ) 25 § Flammability according to
f ·? ASTM D 1692-67 T

ν burn distance / mean value (cm) 6.0

χ Average extinguishing time (sec.) 35 _ >>

| i self-assessment

j ^! going out

Example 16

100 parts by weight of a glycerol started polypropylene triol which was modified with ethylene oxide so that terminal 28% primary hydroxyl groups ^; result with an OH number of 56,

2.5 parts by weight of water ^!)

0.20 part by weight of endoethylene piperazine 0.1 part by weight of pentamethyl diethylenetriamine : 1.0 part by weight of alkyl / phenyl siloxam 1

are mixed with one another and with 42.0 parts by weight of a polyisocyanate containing biuret groups, which has been prepared by reacting a mixture of 2,4- and 2,6-tolylene diisocyanate (isomer ratio 65:35 percent by weight) and water (NCO content 38.5%) ), brought to reaction. 4 ,

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 wi

100 parts by weight of a glycerine-started polypropylene triol which is modified with ethylene oxide in this way it was found that in 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 time to extinguish (sec.) 42

Self-extinguishing assessment

Example 18

100 parts by weight of a glycerine-started polypropylene triol which is modified with ethylene oxide in this way it was found that in 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 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 polyisocyanate containing biuret groups, which is obtained by reaction 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 ) 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

Self-extinguishing assessment

example

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 resulted with an OH number of 28,

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 *) 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 Average deletion time (sec.) 28 judgement self going out

Example! 20th

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 Ν, Ν-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:

Density according to DIN 53 420 (kg / m ') 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

Example 21

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 Characteristics:

Density according to DIN 53 420 (kg / m ^J ) 46 Tensile strength according to DIN 53 571 (kp / cm>) 0.7 Elongation at break according to DIN 53 571 (%) 120 Compression test according to DIN 53 577 (p / cm ^; ) 30th Flammability according to ASTM D 1692-67 T Burning distance / mean value (cm) 4.2 Mean time to extinguish (sec.) 30th judgement self going out

Example 22

100 parts by weight of a started on trimethylolpropane polypropylenetriol, the so with ethylene oxide π was modified so that about 60% primary at the end 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

are with 48.5 parts by weight of a polyisocyanate containing biuret groups, which by reaction

2) use of a mixture of 4,4'- and 2,4'-diphenylmethane diisocyanate, Isomer ratio 60:40 percent by weight, and water has been produced (NCO content 30.0%), caused to react. A foam is obtained with the following mechanical

ii) niche properties:

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

Example 23

100.0 parts by weight of one started on hexanetriol Polypropylenetriol, which has been modified with ethylene oxide in such a way that approx. 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 0.7 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) J, 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) produced, 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 Polypropyleniriols, 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
0.5 parts by weight of endoethylene piperazine 1.0 parts by weight of N, N-dimethylbenzylamine 1.3 parts by weight of alkyl / phenyl-siloxane 3

are mixed with one another 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) produced, reacted.

A foam with the following mechanical properties is obtained:

Density according to DIN 53 420 (kg / m ³ ) 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 Mean time to extinguish (sec.) 35 judgement self going out

Example 26

100.0 weight part of one started on propylene glycol Polypropylene glycol, which has been modified with ethylene oxide so that the terminal ends are about 60% primary Hydroxyl groups with an OH number of 28 resulted,

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

are mixed together and with 55.60 parts by weight 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 / rn- ¹ ) 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 was that at the end about 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 N, N-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

with 37.5 parts by weight of isocyanate adducts (NCO content 35%), from trimethylolpropane and 2,4- and 2,6-toluylene 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 / n ^) 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 hexanetriol and modified with ethylene oxide it was found that about 60% of the primary hydroxyl groups at the end had an OH number of 35.0.

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

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

B) Preparation of the polyisocyanate

134 parts of trimethylolpropane are added in the course of about 1 hour to the initially charged toluene-2,4- and 2,6-diisocyanate (isomer ratio 80:20) heated to 80.degree. C., the reaction mixture heating to 114.degree. After an NCO content of 41.3% has been reached 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 reading of an allophanate polyisocyanate in toluylene diisocyanate isomer mixture with a content of 38.1% NCO at a viscosity of 77 cP ₂₅ c-

100 parts of 2,3-dibromopropanol-1 are added to 1900 parts of this solution at 80 ^° C. and reacted at 90 ^° C. for _{2 hours for 2 hours.} The modified allophanate polyisocyanate in a mixture of toluene diisocyanate isomers is characterized by an NCO content of 35.1%, a viscosity of 118 cP25-c and a solids content of 4%.

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 *) 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

Assessment 'yourself

going out

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-Gchalt 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 ToluyIen-2,4- and -2,6-diisocyanate (isomer ratio 80: 20) added to give the reaction mixture to 114 ° C heated. 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 a content of 38.1% NCO at a viscosity of 77 cP ₂₅ c

100 parts of 2,3-dibromopropanol-1 are added to 1900 parts of this solution at 80.degree. C. and the mixture is reacted at 90.degree. C. for _{2/2 hours} % NCO, a viscosity of 118 CP25 c and solids content of 41%.

A foam is obtained with the following mechanical

niche properties:

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

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

Elongation at break according to DIN 53571 (%) 130

Compression test according to DIN 53577 (p / cm- ¹ ) 30 flammability according to
ASTMD 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 submitted, heated to 8O ⁰ C tolylene 2,4- and 2,6-diisocyanate (isomer ratio 80: 20) added to give the reaction mixture to 114 ° C heated. After reaching a content of 41.3% NCO immediately after the end of trimethylolpropane; -, lolpropanzugabe is heated to 150 ⁰ C and left for 20 hours at this temperature. 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

4-, elongation at break according to DIN 53571 (%) 120

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

Burning distance / mean value (cm) 4.0

, (ι Average extinguishing time (sec.) 42

Self-extinguishing assessment

Example 31

, -, A) 100.0 parts by weight of one based on dipropylene glycol started polypropylene glycol, which was modified with ethylene oxide so that terminal 60% primary Hydroxyl groups with an OH number of 28.0 resulted,

^b "2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine 0.4 part by weight of N-ethylmorpholine 0.4 parts by weight of triethylamine 13 parts by weight of alkyl / phenyl-siloxane 1

are mixed together and with 37.0 parts by weight of an allophanate polyisocyanate (NCO content 35.1%) reacted.

B) Preparation of the polyisocyanate

134 parts of trimethylolpropane are heated in the course of about 1 hour to presented at 8O ⁰ C tolylene-2,4- and -2,6-diisocyanate (isomer ratio 80: 20) was added, with the reaction, mixture to 114 ° C warmed up. After reaching a content of 41.3% NCO immediately after the end of the trimethylol propane was heated to 15O ⁰ C and left for 20 hours at this temperature. The result is a solution of an allophanate polyisocyanate in a mixture of toluene diisoeyanate isomers with an NCO content of 38.1% and a viscosity of 77 cP ₂₅ o

100 parts of 2,3-dibromopropanol-1 are added to 1900 parts of this solution at 80 ^{° C. and the mixture is reacted at 90 °} C. for 2½ hours. 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 ^) 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

Flammability according to

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

33

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:

Density according to DIN 53420 (kg / m ^! ) 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

4.9
35

self-extinguishing

example

m A) 100 parts by weight of a started on glycerol Polypropylenetriol, which has been modified with ethylene oxide so that 80% primary hydroxyl groups at the end with an OH number of 31, 5 parts by weight of a polyester with an OH number of 370, produced from

Ii 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 reacted with 50.1 parts by weight of the polyisocyanate subsequently described in 2 ^r> a closed mold for the reaction.

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 adding 1 part by weight of ß-phenylethylethyleneimine, the mixture is heated to 130.degree. 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 by weight of methyl p-toluenesulfonate.

After dilution with 624 parts by weight of a mixture of 2,4- and 2,6-toluylene diisocyanate (80:20 Percent by weight) a polyisocyanate solution is obtained which has an NCO content of 38.4%, is marked.

A foam with the following mechanical properties is obtained:

Density according to DIN 53420 (kg / m ^! ) 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 / mean value (cm) 4.0 Mean time to extinguish (sec.) 39 judgement self going out

Claims (2)

Patent claims: 1. Process for the production of flame-retardant, non-shrinking, open-pored, urethane groups showing 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 R ₁ SiOf Si - OfSiR, i
SiR, is used in which R is an aliphatic hydrocarbon radical with fewer 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 are contained in the mixture at most in proportions of 25 percent by weight, with a = 2 in proportions of 20 percent by weight at most 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, which by reacting polyisocyanates with active Polyols containing hydrogen atoms are widely used, for. B. in the field insulation, for the production of structural elements or for upholstery purposes. The possible uses of the foamed polyurethanes are, however, due to their flammability when high Temperatures and / or fire limited. It is known that foams containing urethane groups which have flame-retardant properties, from compounds with active hydrogen atoms, preferably polyols, polyisocyanates, water unc. jer 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 be added, which make the flammability of the foam more difficult. 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 23.10 "Flame-Retardant Substances", Plastics Handbook, Vie weg - H ö c h 11 e η, Volume VlI, 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. For example, the introduction of a hygroscopic causes 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", z. B. Solutions of polyisocyanates containing biuret groups in polyisoxyanates and / or solutions free from biuret groups of at least two NCO groups and at least one Ν, Ν'-disubstituted allophanoic acid ester group 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