DE2502658A1 - PROCESS FOR THE MANUFACTURING OF COLD-CARDING FOAMS CONTAINING URETHANE GROUPS - Google Patents

Description

Process for the production of cold-curing foams containing urethane groups

Foams containing urethane groups that are produced by reaction

of polyisocyanates with special

Polyols obtained are widely used, e.g. the field of insulation, for the production of the structural elements.

or for upholstery purposes.

It is known to produce cold-curing foams containing urethane groups from compounds with active hydrogen atoms, preferably polyols, polyisocyanates, water and / or other blowing agents in the presence of emulsifiers, auxiliaries and catalysts and flame-retardant additives in molds. The task of the emulsifiers and stabilizers in the reaction mixture is to homogenize the reactants and to facilitate the foaming process that begins at the same time and to prevent the foams from collapsing after the gas formation has ended. The catalysts are intended to ensure that the processes taking place during the formation of the foam are brought into the desired equilibrium and take place at the correct speed.

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Pur the production of cold-curing, urethane groups Foams with the desired physical properties often contain at least two hydroxyl groups containing polyethers, in which mi ", at least about 10 $ the OH groups present are primary OH groups and have, for example, a molecular weight of 750-100,000, preferably 4-000 to 10,000, e.g. in combination with special polyisocyanates.

So-called "modified polyisocyanates", e.g. solutions of biuret groups, come as special polyisocyanates Polyisocyanates in polyisocyanates free of biuret groups and / or solutions of at least two NCO groups and at least one N, N'-disubstituted allophanoic acid ester group containing polyisocyanates in allophanic acid ester groups-free polyisocyanates and / or "solutions of polyisocyanates containing urethane groups in urethane group-free polyisocyanates and / or solutions of polyisocyanates containing isocyanuric acid rings in Isocyanurate group-free polyisocyanates in question.

The cold-setting, urethane-grouped foams having desirable physical properties for example using the "modified polyisocyanates", however, often have the disadvantage that sLe, in particular during foaming by shaping, defects in the form of bubbles under the foam surface show up can also propagate into the interior of the molded part. This appearance is extremely disadvantageous, for example in the Manufacture of molded parts, be it for the furniture industry or the automotive industry, as these are based on fine upholstery fabrics

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BATH ORIGINAL

Blistering clearly visible. This can be achieved by using commercially available polysiloxane-polyalkylene oxide copolymers cited malfunction cannot be remedied, since in this case, even with the smallest amounts of stabilizers, a irreversible shrinkage occurs and becomes unusable Foams leads.

Attempts have already been made by using special Silicon compounds to remedy the described problem in the production of polyurethane foam (see German Offenlegungsschriften 2 232 525, 2 337 140 and 2 246 400). However, these attempts have not yet led to all-round satisfactory results in practice. In particular It has been shown that even when the silicon compounds described in more detail in the laid-open specifications are also used often a shrinkage of the foam is not completely avoided can be.

There has now been a method of making no shrinking, cold-setting, urethane group-containing foams, which is based on the use of special silicon compounds based, whereby the disadvantages can be avoided and the Production of perfect foams succeeds.

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The present invention thus provides a process for the production of cold-curing, non-shrinking, Foams containing urethane groups by foaming a mixture of at least two hydroxyl groups containing polyethers of molecular weight 750 to 100,000, polyisocyanates, water and / or organic blowing agents, silicon compounds and optionally catalysts "and other auxiliaries, characterized in that the silicon compounds are those of the general formula

R ¹
R ^ SiO / TSi-O ^ SiR,

R is an alkyl radical with 1 to 3 carbon atoms, preferably

R is an aryl radical with 6 to 14 carbon atoms, preferably

R _{2 is} an aryl radical with 6 to 14 carbon atoms, preferably CgH ₅ -, or a group R ¹

^ means and

where _Ώ 1

-τ

wid fü di /

again for the group Z = O-Si ^ OSiR, x is a number from 1 to 20, and

y is a number from 0 to 10, where within different values for y of the molecule. may occur,

and the total number of Si atoms in the molecule does not exceed 6o, be used.

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The silicon compounds to be used according to the invention are known and can, for example, according to the teaching of the German Patent specification 1 046 049 or the German Auslegeschrift 2 135 674 can be obtained.

Typical examples of those to be used in the present invention Silicon compounds are:

^C 6 ^H 5

(CH,), Si-O-Si-O-Si (CH,),

DD t DD

° 6 ^H 5

(CH,), SiCfSi-O

DD

Si (CH ₃ ) ₃ '3

(CH ₃ ) ₃ SiO

Si

0
Si

-O-

Si

Si

0 Si

OSi (CH ₃ ) ₃

-Si-OSi (CH ₅ ;

OSi (CH,),

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Surprisingly, the following technical advantages have also been shown according to the invention!

1. The mixtures of silicon compounds used according to the invention are soluble in the polyols used and thus avoid storage difficulties. The dissolved additional sides promote the flow behavior and the formation of nuclei during the foaming process, which in the case of the Production of foams by shaping with long flow paths or strongly changing cross-sections Is a prerequisite for optimal production.

2. With the usual foaming conditions and formulation structure highly elastic molded parts can be obtained with an extremely good grip, i.e. the impression characteristics is favorably influenced.

3. The graduated effectiveness of the silicon compounds used according to the invention as a function on the number of siloxy units * The invention In this way, additives can also be adapted to changed recipes without any difficulties, wherein the gradable stabilizing effect brings the additional advantage that the forces to Reduce the pressure of molded foams to a minimum.

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Starting components to be used according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as described, for example, by W. Siefken in Justus Mebigs Annalen der Chemie, 562, pages 75 to 136, for example ethylene diisocyanate, 1,4 -Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, i-isocyanato ^^^ - tri methyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, American patent 3 401 190), 2,4- and 2,6-hexahydrotolylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -4 , 4- phenylene diisocyanate, perhydro-2,4'- and / or - ^^ '- diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, Diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene ^ 1,5-diisocyanate, tri phenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and described, for example, in British patents 874 430 and 848 671, m- and p-isocyanatophenylsulfonyl -isocyanates according to the ais - "ikanisehen patent 3 454 606, perchlorinated aryl polyisocyanates, as described, for example, in German patent specification 1 157 601 (American patent 3 277 138 /, carbodiimide-containing polyisocyanates, as described in German patent 1 092 007 ( US Pat. No. 3,152,162) , diisocyanates as described in US Pat. No. 3,492,330, polyisocyanates containing allophanate groups, such as those described, for example, in British Patent 994 890, Belgian Patent 761 626 and the published Dutch Patent Application 7 102 524 are described containing isocyanurate groups

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Polyisocyanates, as described, for example, in American patent 3 001 973, in German patents 1 022 789, 1 222 067 and 1 027 394 and in German Of fenlegungs documents 1 929 034 and 2 004 048, polyisocyanates containing urethane groups, such as they are described, for example, in Belgian patent specification 752 261 or in American patent specification 3 394 164, polyisocyanates containing acylated urea groups according to German patent specification 1 230 778, polyisocyanates containing biuret groups, as described, for example, in German patent specification 1 101 394 (American patents 3 124 605 and 3,201,372) and in British patent specification 889 050, polyisocyanates prepared by telomerization reactions, as described, for example, in American patent specification 3,654,106, polyisocyanates containing ester groups, as described, for example, in British patents 965,474 and

1,072,956 , in the American patent 3,567,763 and in the German patent 1,231,688, reaction products of the above-mentioned isocyanates with acetals according to the German patent 1,072,385 , and polyisocyanates containing polymeric fatty acid residues according to the American patent 3,455,883.

It is also possible to use the isocyanate group-containing distillation residues obtained in the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates to be used. It is also possible to use any desired mixtures of the aforementioned polyisocyanates to use.

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As a rule, the technically easily accessible polyisocyanates, e.g. 2,4- and 2,6-tolylene diisocyanate, are particularly preferred and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene-polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation are produced ("raw MDI") and carbodiimide groups, urethane groups, Allophanate groups, isocyanurate groups, urea groups or polyisocyanates containing biuret groups ("modified polyisocyanates").

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Monofunctional isocyanates such as prop / 1 isocyanate, cyclohexyl isocyanate, phenyl isocyanate, toluyl isocyanate, p-chlorophenyl isocyanate can also be used. However, their proportion should not be more than 20% of the isocyanate combination used according to the invention, based on the isocyanate content.

The starting material for the process according to the invention are also at least two, usually two to eight, preferably two to three, hydroxyl-containing polyethers, usually with a molecular weight of 750-100,000. Such polyethers, known per se, are z. B. by polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide _f tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for. B. in the presence of boron trifluoride, or by adding these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols or amines, eg. B. water, ethylene glycol, propylene glycol (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine, ethylenediamine. Often those polyethers are preferred which predominantly (up to 90% by weight , based on all OH groups present in the polyether) have primary OH groups. Polyethers modified by vinyl polymers, such as those used, for. B. by polymerization of styrene, acrylonitrile in the presence of polyether (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German patent 1,152,536) are also suitable, as are polybutadienes containing OH groups.

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Among the polythioethers are in particular the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols are listed. Depending on the co-components The products are polythio mixed ethers, polythioether esters, polythioether ester amides.

The polyethers mentioned can also be modified by reaction with less than equivalent amounts of polyisocyanate will.

The higher molecular weight polyethers to be used according to the invention can also be used in mixtures with low molecular weight compounds with active hydrogen atoms of molecular weight up to 750 or in mixtures (up to 50% by weight , based on the polyether) with other higher molecular weight compounds with active hydrogen atoms. Particularly suitable low molecular weight compounds with active hydrogen atoms are compounds containing hydroxyl groups. For example, ethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerol, 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, on such low molecular weight compounds with active hydrogen atoms or on water. Other higher molecular weight compounds with active hydrogen atoms are the compounds known per se, such as polyesters, polyacetals, polyethers, polyester amides, polycarbonates.

As polyacetals, for. B * the compounds which can be prepared from glycols such as diethylene glycol, triethylene glycol, 4,4 ^I- dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde are in question. Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.

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Polycarbonates containing hydroxyl groups are those of the type known per se. B. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, Triethylene glycol, tetraethylene glycol with diaryl carbonates, z. B. diphenyl carbonate or phosgene can be produced.

The polyester amides and polyamides include, for. B. those from polyhydric saturated and unsaturated amino alcohols, Predominantly linear condensates obtained from diamines, polyamines and their mixtures.

Also polyhydroxyl compounds already containing urethane or urea groups and optionally modified ones natural polyols such as castor oil, carbohydrates, starch can be used. Also addition products of alkylene oxides on phenol-formaldehyde resins or also on urea-formaldehyde resins can be used according to the invention.

Representatives of these compounds to be used according to the invention are, for. B. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology ¹¹ , written by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, pages 5-6 and 198-199, and in the Kunststoff-Handbuch, Volume VII, Vieweg-Höchtlen, Carl Hanser-Verlag, Munich, 1966, e.g. on pages 45-71.

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According to the invention are water and / or highly volatile organic substances are used as propellants. Organic blowing agents include acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, Monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, also butane, hexane, heptane or diethyl ether are possible. A propellant effect can also be achieved by adding at temperatures above room temperature with the elimination of gases, for example nitrogen, decomposing compounds, e.g. azo compounds such as azoisobutyronitrile will. Further examples of propellants as well as details on the use of propellants can be found in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.

According to the invention, catalysts are also often used. Catalysts which can also be used are those of the type known per se, for example tertiary amines, such as triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine, N, N, N ¹ , N'-tetramethyl-ethylenediamine , 1,4-diaza-bicyclo- (2,2,2) -octane, N-methyl-N'-dimethylaminoethyl-piperazine, Ν, Ν-dimethylbenzylamine, bis- (N, N-diethylaminoethyl) adipate, Ν, Ν-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, Ν, Ν, Ν ', Ν ^1- tetramethyl-1,3-butanediamine, Ν, Ν-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole ^ 2-methylimldazole. Mannich bases known per se and composed of secondary amines, such as dimethylamine, and aldehydes, preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone, cyclohexanone and phenols, such as phenol, nonylphenol, bisphenol, are also suitable as catalysts.

Tertiary amines containing hydrogen atoms active towards isocyanate groups as catalysts are e.g. Triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyl-diethanolamine, n, N-

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Dimethyl ethanolamine and their reaction products with Alkylene oxides such as propylene oxide and / or ethylene oxide.

SiIf, mines with carbon-silicon bonds are also used as catalysts, as described, for example, in German patent specification 1 229 290 (corresponding to American patent specification 3,620,984) are in question, e.g. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl tetrame ethyl disiloxane.

Nitrogen-containing bases such as tetraalkylammonium hydroxides and alkali metal hydroxides such as Sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate are suitable. Also hexahydrotriazines can be used as catalysts.

According to the invention, organic metal compounds, in particular organic tin compounds, can also be used as catalysts be used.

Tin (II) salts are preferably used as organic tin compounds of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the tin (IV) compounds, e.g., dibutyl tin oxide, dibutyl tin dichloride, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyltin diacetate into consideration. It goes without saying that the abovementioned old catalysts can be used as mixtures will.

Further representatives of catalysts to be used according to the invention and details about the mode of action of the catalysts are in the Kunst st off handbook, Volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 96 to 102.

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The catalysts are generally used in an amount between about 0.001 and 10 % by weight, based on the amount of compounds having at least two isocyanate-reactive hydrogen atoms and a molecular weight of 400 to 100,000.

According to the invention, surface-active additives, such as emulsifiers, can also be used.

The sodium salts of castor oil sulfonates, for example, are used as emulsifiers or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine in question. Also alkali or ammonium salts of Sulfonic acids such as from dodecylbenzenesulfonic acid or Dinaphthylmethanedisulfonic acid or of fatty acids like e Ricinoleic acid or polymeric fatty acids can be used as surface-active Additives are also used.

The main foam stabilizers are polyether siloxanes, especially water-soluble representatives, in question. These compounds are generally constructed in such a way that a copolymer consists of Ethylene oxide and propylene oxide with a polydimethylsiloxane residue connected is. Such foam stabilizers are described, for example, in American patents 2,834,748 and 2,917 and 3,629,308.

According to the invention, reaction retarders, for example acidic substances such as hydrochloric acid or organic acid halides, and cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes, and pigments or dyes and flame retardants of the type known per se, e.g. tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate, can also be used and polyphosphates, stabilizers against aging and weathering, plasticizers and substances with a fungi and bacteriostatic effect, fillers such as barium sulfate, kieselguhr, carbon black or whiting chalk can also be used. _Le A 16 154 .15-

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Further examples of optionally also to be used according to the invention surface-active additives and foam stabilizers as well as cell regulators, reaction retarders, Stabilizers, flame-retardant substances, plasticizers, dyes and fillers as well as fungistatic and bacteriostatic Active substances as well as details about the use and mode of action of these additives are in Art st off manual, Volume VI, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on the Pages 103 to 113 described.

The reaction components are according to the invention after one-step process known per se, the prepolymer process or the semi-prepolymer process, webai one often makes use of machine facilities, e.g. those in the American patent specification 2,764,565. Details of processing facilities, which are also suitable according to the invention are in the Kunst st off manual, Volume VI, published by Vieweg and Höchtlen, Carl-Hanser-Verläg, Munich 1966, e.g. described on pages 121 to 205.

In the foam production according to the invention

^ preferably »
Foaming "*" ~ y ~ carried out in molds. The reaction mixture is introduced into a mold. Metal, for example aluminum, or plastic, for example epoxy resin, can be used as the molding material. The foamable reaction mixture foams up in the mold and forms the molded body. The foam molding 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. According to the invention, one can proceed in this connection in such a way that enough foamable reaction mixture is introduced into the mold that the foam formed just fills the mold. But you can also work in such a way that you get more foamable

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Reaction mixture enters the mold than for filling the inside of the mold with foam is necessary. In the latter case, "overcharging" is used; such a procedure is e.g. from the American Patents 1,178,490 and 3,182,104 are known.

In the case of foam molding, there are many known ones "External release agents", such as silicone oils, are also used. But you can also use so-called "internal release agents", if appropriate in a mixture with external release agents, such as those from German Offenlegungsschriften 2 121 670 and 2,307,589 have become known.

According to the invention, cold-curing foams are produced (cf. British Patent 1,162,517, German Offenlegungsschrift 2,153,086).

Of course, the production is also according to the invention of free-foamed foams possible.

The products obtainable according to the invention find the applications known per se, for example as upholstery materials.

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Manufacturing and Isolisrungsvorschrift for the fiction according to to be used silicon connection . -Lengths

According to the teaching of German patent specification 1 046 049 produced a mixture of polymer homologous phenylmethylpolysiloxanes.

Work-up instruction A;

The mixture is broken down by fractional distillation through a packed column. There will be the following Fractions of silicon compounds of the general formula

Ji (CH ₃ ) ₃ (1 a)

0
Si (CH ^)

caught:

1. 90 ° C / 1 mmHg

Composition: χ = 0

χ = 1

2.158 ^° C / 0.8 mmHg

3. 195 ° C / 0.3 mmHg

2.5 percent by weight 97.5 percent by weight

X = 1 1 Weight percent X ⁼ 2 98 5 percent by weight X = 3 0, 5 percent by weight X = 2 10 Weight rating X = 3 85 Weight sprο ζ ent higher Homologues 5 Weight percent

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BATH ORIGINAL

Processing instructions B

The mixture of polymer homologous phenylmethylpolysiloxanes is broken down by distillation without a fraction column. First, a forerun is taken off under normal pressure up to 150 ^° C. in the distillation bottom. Then distilled all at a pressure of 0.5 mmHg to 255 ⁰ C bottom temperature volatile fractions. The distillate has the following composition:

Silicon compounds of "J χ = 1 64 percent by weight

aforementioned general V _x -P 2P ^ Gpwirh + «coins + rormex \\ β.) with ι

J x = 3 3.3 percent by weight

According to the gel chromatogram, the residue consists mainly of silicon compounds of the formula (1 a) with χ = 3 as well as the next higher homologue, while even higher Homologues with up to approx. 22 Si atoms are only contained in amounts totaling 10 percent by weight. The middle one Molecular weight of this residue (number average) is approx. 1000. That obtained under reduced pressure The distillate and the residue are mixed in a ratio of 55:45 parts by weight.

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Examples

a) Pie 5 examples listed below were below

'' identical process and test conditions carried out :

Temperature of the components: +25 C speed of the stirrer: 2000 rpm

Mixing time: 10 see

Dosing accuracy

Polypropylene glycol, isocyanate: +0.1 g Water, silicon compound

Diazabicyclo-2,2,2-octane Triethanolamine and triethylamine

+ 0.002 g

b) The stated flow resistances were determined according to Dow air flow method is determined in mm of water column (mm Ws) and is a measure of the open cells.

The pressing forces were measured on the test specimen in accordance with DIN 53 577 (compression test) as the differential pressure between the first The upsetting process on the virgin material and the fourth upsetting process are determined. They are thus largely regardless of the bulk density.

example 1

A. 100 parts by weight of a trimethylolpropane started polypropylene glycol, which has been modified with ethylene oxide so that terminal 60 % primary hydroxyl groups result with an OH number of 35, 2.5 parts by weight of water
0.6 part by weight of ttiazabicyclo-2,2,2-octane 1.0 part by weight of triethanolamine 1.0 part by weight of triethylamine

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B. 1.0 parts by weight of the silicon compounds of the formula (1 a) with χ = 1 obtained according to work-up instruction A are mixed and old

C. 41.4 parts by weight of an isocyanate mixture which

40 percent by weight of a toluene diisocyanate mixture (2,4- and 2,6-isomers in the ratio 65:35) and
60 percent by weight of a polyphenyl-polymethylene polyisocyanate (viscosity about 200 cP at 25 ⁰ C)
is made to react in a form. The polyphenyl-polymethylene-polyisocyanate was obtained by anuil-formaldehyde condensation with subsequent phosgenation.

D. A foam with the following mechanical properties is obtained

Characteristics: DIN 53420 (kg / m ³ ) 45 Bulk density DIN 5357t (KPa) 60 Tensile test DIN 53571 W. 100 Elongation at break DIN 53577 (KPa) 2.0 Attempt to print (mm Ws) 30th Flow resistance (N) 8th Pressing force medium fine Pore structure

Example 2

Δ. The polyether mixture described in Example 1 under A,

B. 1.0 part by weight of the silicon compounds of the formula (1 a) obtained according to work-up instruction A with x. = 2 are mixed and with

C. 41.4 parts by weight of one described in Example 1 under C. Isocyanate mixture brought to reaction.

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A foam with the following mechanical properties is obtained:

Flow resistance (mm Ws) 50 Pressure force (N) 25 Fine pore structure

Example 5

A. The polyether mixture described in Example 1 under A.

B. 1.0 part by weight of the silicon compounds obtained under work-up instruction A with formula (1 a) χ = 3 are mixed and with

C. 41.4 parts by weight of one under Example 1 under C. isocyanate mixture described brought to reaction.

D. A foam with the following mechanical properties is obtained:

Flow resistance (mm Ws) approx. 300 Pressing force (N) approx. 60

Very fine pore structure

Example 4

A. The polyether mixture described in Example 1 under A.

B. 0.3 parts by weight of that described in Example 3 Silicon compound are mixed and with

C. 41.4 parts by weight of one described in Example 1 Isocyanate mixture brought to reaction.

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D. A foam with the following mechanical properties is obtained:

Flow resistance (mm Ws) Pressing force (N)

Example 5

A. The polyether mixture described in Example 1 under A,

B. 1.0 part by weight of the silicon compound obtained according to work-up instruction A according to formula (1 a) with the following composition:

χ = 1 80 percent by weight χ = 2 15 percent by weight χ = 1.25 χ = 3 5 percent by weight

are mixed up and with

C. 41.4 parts by weight of one described in Example 1 under C. Isocyanate mixture brought to reaction.

D. A foam with the following mechanical properties is obtained Characteristics:

Flow resistance (mm Ws) 30th - fine Pressing force (N) 8th Pore structure middle one

Examples 1-5 show that it

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9M

a) by the choice of the silicon compound used according to the invention or

t>) by changing the concentration of this compound

c) by suitable mixing of these compounds or

d) by combining the measures a) - c), the open cells and the pressing forces are outstandingly possible and adjust the pore structures of the foams specifically and in a wide range in a tailor-made manner. The activity during foam production (start time, rise time, setting time) is not affected.

Example 6

A. 100 parts by weight of a trinethylolpropane started polypropylene glycol, which was modified with ethylene oxide so that terminal 60 % primary hydroxyl groups with an OH number of 28 result, 3.2 parts by weight of water,

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

B. 0.1 part by weight of the work-up instructions B obtained methylphenylpolysiloxane are mixed, and

C. 39.0 parts by weight of the isocyanate described below reacted in a closed form:

To a mixture of 225 parts of a mixture of 80 percent by weight, 2.4 and 20 percent by weight 2,6-tolylene diisocyanate and 274 parts of 4,4'-diphenylmethane diisocyanate 20 parts of 1,2-propylene glycol are added at 60 ° C. and over the course of 30 minutes

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implemented in a metal mold. After adding 1 part of ß-phenylethylethyleneimine, the mixture is heated to 130.degree. The trimerization which takes place at this temperature is stopped after 21/2 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 80/20 percent by weight mixture of 2,4- and 2,6-toluene diisocyanate, a polyisocyanate solution is obtained which has the values% -NCO: 38.4; 0P ₂₅ O ₀ 24 n ^ °: 1.5738 is characterized.

D. A molded foam with the following mechanical properties is obtained Characteristics:

Bulk density DIN 53420 (kg / m ³ ) 43 Tensile test DIN 53571 (KPa) 130 Elongation at break DIN 53571 (%) 120 Pressure attempt DIN 53577 (KPa) 3.3

Example 7

A. The polyether mixture described in Example 6 under A,

B *. 1.0 part by weight of the siloxane prepared from trimethylchlorosilane and diphenylchlorosilane according to the manufacturing instructions of molecular weight 361 are mixed and with

C. 39.0 parts by weight of one described in Example 6 under C. Isocyanate mixture brought to reaction.

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D. One obtains a formula with the following mechanical properties:

Bulk density DIiM 53420 (kg / m ³ ) 44 Tensile test DIN 53571 (KPa) 135 Elongation at break DIN 53571 (%) 110 Attempt to print DIN 53577 (KPa) 3.5 Example 8

A. 50 parts by weight of a trimethylolpropane started polypropylene glycol, which was modified with ethylene oxide so that terminal 60 % primary hydroxyl groups result with an OH number of 28 and 50 parts by weight of a trimethylolpropane started polypropylene glycol, which was modified with ethylene oxide so that terminal 70 % primary hydroxyl groups result, which was also grafted with acrylonitrile and styrene in a ratio of 60:40 and had an OH number of 28,

2.7 parts by weight of water,

0.15 parts by weight of diazabicyclo-2,2,2-octane (as catalyst), 0.08 parts by weight of 2,2'-dimethylaminodiethyl ether (as a catalyst) and

B. 0.5 parts by weight of the according to the work-up instructions B obtained methylphenylpolysiloxane are mixed and with

C. 34.0 parts by weight of a tolylene diisocyanate mixture (2,4- and 2,6-isomers in the weight ratio 80 ':, 20%) and 20.0_ parts by weight of a polyphenyl-polymethylene-polyisocyanate, which has been obtained by aniline-formaldehyde condensation and subsequent phosgenation, reacted in a form.

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D. A molded foam having the following mechanical properties is obtained Characteristics:

Density DIN 53420 (kg / m ³ ) 43

Tensile test DIN 53571 (KPa) 170

Elongation at break DIN 53571 (%) 170

Compression test DIN 53577 (KPa) 4.1-

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Claims (1)

Claim: Process for the production of cold-curing ,, no shrinking foams containing urethane groups f_ by foaming a mixture of at least two Molecular weight polyethers containing hydroxyl groups 750 to 100,000, polyisocyanates, .water and / or organic Blowing agents, silicon compounds and optionally catalysts and . further auxiliaries, characterized in that the silicon compounds are those of the general formula IUSiO / ^ Si -0-7 SiR J - to ^X - whereby R is alkyl of 1 to Jt C atoms, preferably CH, - R ^{1 is} an aryl radical with 6 to 14 carbon atoms, preferably R _{0 is} an aryl radical with 6 to 14 carbon atoms, preferably Cz-Hc- "or a group R / ^ O-Sij ^ OSiR, means and B? where R R in turn stands for the group / ^ O -Si _-1 T ^ OSiR, χ a number from 1 to 20, and y denotes a number from 0 to 10, different values for y within the molecule. appear can, and the total number of Si atoms in molecule 60 does not exceed increases, can be used. Le A 16 154 - 28 - 609832/0761