DE1911645C3 - Process for the production of polyurethane foams - Google Patents

Description

»Should be dight percent, based on the treated material. In contrast to this, the proportion of the foam at whose phase interfaces the reactions according to the invention take place is very small. The essential distinguishing feature of the known impregnation and constituent processes for foams, however, is their course under conditions which do not give rise to new spaces and cells. In contrast, according to the invention, ethylene chloride, chloroform, cyclohexane, butyl acetate,
Cyclohexane, methyl isobutyl ketone, benzene, chlorobenzene, nitrobenzene, decalin, petrol hydrocarbons,
Trichlorethylene, tetrachloroethane, trichloroethanol, di-5methyl sulfoxide, dimethylformamide, tetramethylurea, methanol, ethanol, isopropanol or butanol,
increase. The most varied of crystallized polyisocyanates, such as 1,5-naphthalene diisocyanate
or 4,4'-diisocyanatodiphenylmethane can be used in

According to the process, new space, and without the need for high concentrations in blowing agents at room temperature, through irreversible fixing liquid polyisocyanates or their solutions, such as the tension and swelling processes of the matrix
in the case of rapid changes in the state of the react

tion partner created by their molecular growth.

ζ. B. the various isomer mixtures of Toluylencliisocyanates, be solved, so that an extraordinarily large number of reactants and

According to the procedure according to the invention, solvents for swelling and for producing accordingly, many reactive components are made available through stress processes in the matrices arrange a matrix spatially 2 a and stand spatially further. It should be noted that addition is also to be expanded, with this regulating effect overproducts of the most diverse polyisocyanates at Diraschend can be maintained for a long time, so that or triols, as well as biuret polyisocyanates, are semi-open-celled Foams can be obtained in 20 carbazide, urea, alophanate or acylated of which the cell-shaped biuret polyisocyanates according to the invention are not used in these monomers Substance components have a multiple of the usually high solubility and therefore high used matrix. Basic pre-reactive mixtures of relatively low viscosity Settlements for the implementation of the new process for the compression and generation of tensions in the are quick and with considerable heat as matrices are available. The tinting isocyanate reactions which both quench almost instantaneously, especially when the formation of largely linear or strongly divergent polyisocyanates or their mixtures and solvent components and cross-linked materials with polyurethane, poly- solutions are sucked into the matrices, urea, polybiuret, allophanate, acylamide, car- Through rapid reactions such. B. Poly-

Bodumid, uretdione or isocyanate structures lead to merizations of these polyisocyanates and become swellable. lungs and tension that has occurred in the matrix

The subject matter of the invention is thus a method that is fixed in a reversible manner. Cell enlargement and opening becomes to modify polyurethane foams in this process variant by rapid by treatment with polyisocyanates, thereby changing the physical state of the monomers in the sense of: indicates that polyisocyanates are either irreversible with 35 (liquid, monomer -> ■ solid, polyisocyanurate) fixed by themselves or with connections with reactive and thus at the same time space for the disqualified Hydrogen atoms and / or ethylenically un- standing polyisocyanurates created, whereby by saturated compounds in the presence of catalysts are obtained in the capillary spaces and on the phase foams in which the poly-boundary surfaces largely open-cell urethane and / 40 merization brought component a multiple z. B. or urea and / or isocyanurate groups can be up to 800 to 900 <of the matrix weight, pointing foams, the amount of when using the above-mentioned polyiso-

Polyisocyanates and, if appropriate, compounds with cyanates or their mixtures or their addition-reactive compounds Hydrogen atoms at least 15 products of higher molecular weight polyols from the weight percent of the original foam, the average molecular weight was 500 to 10,000 wearing. with terminal and possibly lateral

Technically important reactants according to Er- NCO groups (NCO prepolymers), it is therefore possible to find those as they are, for. B. in the basic in a targeted manner, e.g. B. following the poly work on the diisocyanate polyaddition process urethane foam production, by choosing the most varied reactants from O. Bayer and coworkers in Ang. Chemistry 62, 50 a selected matrix 57 to 66 (1950), Ang. Chemistry 64, 523 to 531 (1952), to be modified so that either highly elastic, high-O. B ayer, The Diisocyanate Polyaddition Process,
Carl-Hanser-Verlag, Munich, 1963, also in colors,
Lacquers, paints 2, 123 to 128 (1948), plastics 41, 13 to 19 (1951), are mentioned.

Many technically important polyisocyanates of the aliphatic, cycloaliphatic, araliphatic or
aromatic series, as z. B. by W. S iefke η
in Ann. d. Chem. 562, 75-136 (1949)
are, are thin-viscous liquids that, like 60, substance types. has been found to be excellent swelling agents for the

various open-cell polyurethane foams matrix with di- or triols. higher molecular weight poly

To load hydroxyl compounds, polyamines, polyketimines or polyaldimines and in the second phase 65 an excess amount of any gaseous, liquid, solid or dissolved polyisocyanates in the Bring matrix to their phase interfaces for polyadding polymerization, it being necessary

Refined foams similar to polyurethane elastomers or semi-hard or hard foams can be obtained that have the usual semi-hard and hard foams in open-cell structure, strength, Exceed elasticity, elongation at break many times over. The method according to the invention allows therefore the implementation of a variety of finishing options on a wide variety of polyurethane foam

represent. During these swelling processes, the Matrices are strong in the three dimensions of space

If desired, the swelling effect can be achieved by adding small amounts of organic solvents, such as carbon tetrachloride, acetone, ethyl acetate, meth-

is, the reaction by strong tert. Alkaline bases

phenolate, phosphine, arsine, tin (II) - and tin (IV) - German ^ g

Salts, zinc octoate or common catalysts for thioethers from ^ί ^^^^^ ίΆΛ

Polyaddition *. or polymerization reactions to see Auslegeschrift 1108 903 ^ Hohoinolekulare Bi-

accelerate 5 uretes according to the German Auslegeschriften 12 29 967

A particularly preferred embodiment of the and 1174 759, also isopyamates, which by TeIo-

The method according to the invention consists in the polymerization reactions ethylenically unsaturated compound

isocyanates or the pre-compounds containing NCO groups from a wide variety of polyisocyanates

Polymers have also been prepared in counter-fashion via polymerization reactions, polyisocyanates, such as

waiting for catalysts, ζ. B. with the formation of poly io they can be produced by hydrogenating polyaddition

isocyanurate !! to implement. If one strives for the also the most diverse isocyanate releasers smd

Production of foams of natural rubber type, usable, also containing uretdione groups

of a highly elastic nature, so it is advantageous to use far- polyisocyanates.

going linear, terminal NCO groups containing polyesters, polyethers, polythioethers or poly- 15 in addition to the polyisocyanates optionally compound acetals for the polymerization in the matrix to compare with active hydrogen atoms of any kind, which z. B. from corresponding linear poly question, these advantageous first oil for loading and 1,5-naphthylene diisocyanate, p-phenylene · the matrix are used, such as. B nohermoleisocyanat, 4,4'-diisocyanato-diphenylmethane, 4,4'-di- kulare α, ω-diureas with elasticizing segment isocyanato-diphenyl ethers, l-methylbenzene - ^ - diiso- ao th such. B. from linear hydroxy! Polyesters cyanate or l-methylbenzene-2,4-diisocyanate, Tetra- by reaction with Dnsocyanaten and Nachtragmethylene diisocyanate or hexamethylene diisocyanate borrowed reaction with ammonia have been obtained and which are optionally urine, further sec. Hydroxyl-containing polystyrene or urethane groups as chain-extending epoxides based on 4,4-dihydroxydiphenyl groups in their molecule. They can have average molecular weights of 400 to fizierungsprodukte, modified by grafting reactions and possibly higher molecular weight polyhydroxy compounds adorned in solvents, or in low molecular weight liquid polyisocyanates their hydroxyl group-containing reaction products with or dissolved in dimethylformamide for polymerization, a deficiency of polyisocyanates. furthermore poly reach. Aliphatic, light aldimines or polyketimines, reaction products of true diisocyanates, with which highly alkoxymethyl isocyanates, in particular methoxyelastic foams can be produced, are p-phenethyl isocyanate, with polyols or polyamines, sonylene diisocyanate, hexamethylene diisocyanate, tetra- such as higher molecular weight polyols or polyamines, linear methylene diisocyanate or their adducts with polyols. or branched structure, amino groups or tert. The preferred polyols are polyesters composed of 35 amino group-containing polyethers, hydroxyl group-adipic acid and ethylene glycol or hexanediol or pen or N-methylol groups containing higher molar polycarbonates of hexanediol, polythioether kulare polyurethanes with an average molecular weight of thiodiglycol and hexanediol from 400 to 100, triethylene glycols by weight are also hydroxyl-containing polyethers from tetra-dietbylaniline and its condensation products with hydrofuran or linear polyethylene oxides with hydroxyl formaldehyde, addition products of butyrolactone end groups of average molecular weights 500 and diols, hydrazine or polyamines, methylol to 4000. In this embodiment, further phenols or their condensation by Mannich compounds obtained with technically important modified polyisocyanates such aliphatic amines. Also like NCO groups containing higher molecular weight pre-soluble polyhydantoins, which can be built through their end groups monopolymers of hydroxyl end groups, also so-called storable esteramides, basic polyethers, polythioethers, polyurethanes with hydroxyl or urea or or polycarbonates, also NCO- Groups containing amino end groups, high molecular weight diamines, such as tend, soluble high molecular weight polyurethanes and they also consist of p-nitrophenyl isocyanate and higher polyureas or polybiurets with NCO groups. Molecular polyols and subsequent hydrogenation Phosphoric acid esters, phosphonic ester groups, or can have been produced from polyether polyols by reaction with retaining polyisocyanates, modified isocyanato pressure with ammonia in the presence of nickel adducts of castor oil or drying oils, isocatalysts are cyanatopolythioethers of average molecular weight - suitable. Polyester containing hydroxyl groups by weight from 400 to 10,000 or semicarbazide entamides or polyesters of maleic acid or fumaric polyisocyanates are also suitable. 55 acid with hydroxyl groups, monoalcohols, such as

Outstandingly usable, modified polyiso- methacrylic acid-zJ-hydroxy polyester, as well as polyester

cyanate for carrying out polymerizations in from the Diels-Alder adducts of maleic acid

the matrix are also acylated polyurea- hexachlorocyclopentadiene can also be obtained from

polyisocyanate of the German Auslegeschrift 12 30 778, be interesting, also esters of antimony acid, such as

low molecular weight modification products of cyclo- 60 also hydroxyl-containing phosphoric acid esters, boron

butane diisocyanate of the German Auslegeschrift acid ester or silicic acid ester with which the

11 10 859, the most diverse biuret polyisocyanate matrices can be loaded. Also suitable the German Auslegeschrift 11 01 394, urea and are urethane, urea, amide or tertiary or Urethane diisocyanate mixtures of the German interpretation quaternary amino groups, as well as free carboxyl letters 10 20 327, biuret-modified polyisocyanates 65 groups or sulfonic acid groups containing high der German Auslegeschriften 12 27 003, 12 15 365, molecular polyurethanes in the form of aqueous

12 27 004, 11 65 580, and also polyisocyanates, such as those used in cationic or anionic dispersions for imder German patent 8 83 504 are described, impregnation and loading of the foams incorporated

7 8

are set. Excess diol gets onto the matrices loaded in this way for the same reason iso-

then any polyisocyanates to act, whereby cyanurate polymerizations start, since the over-

Polyadditions or coupled polyaddition polyschüosigc; Glycol amount always wrong! from the

merizations take place. melle is released and therefore educated higher-

Another variant of the method is z. B. therein, polyurethanes containing 5 molecular NCO groups

the foam with water or water-releasing substances under the influence of strong polymerization catalysts

Quickly polymerize compounds or a wide variety of N-methylol- sators.

connections z. B. urea, N-methylol- Another advantageous variant of the process consists of caprolactams, adducts of chloral to urea in the use of alkoxymethyl monoiso- or of acetamide and caprolactam, in large amounts of io cyanates, especially of methoxymethyl isocyanate to be loaded, as well as with N- Methylol compounds of or its addition products to higher molecular weight melamine and dicyandiamide, ie with methylolver- linear », ω-position hydroxyl groups or amino bonds of compounds containing aminoplast but also pheno groups, the compounds capable of plastic formation, as well as with processes of the German Auslegeschrift 12 44 410 on formic acid or polycarboxylic acids or carboxylic 15 are available. The use of iso acid anhydrides and, in the second phase, the various cyanatose oils or acyl isocyanates or solfonyldene polyisocyanates in the matrix with the ver isocyanates can also be advantageous.
to bring bonds to reaction, wherein; B. Another variant of the method consists in the Be-CO ₂ -driving reactions are achieved and also split off semi-hard to 20 formaldehyde condensations by charging matrices with so-called alcohol-discharging formaldehyde condensations, which are made from the group of hardness foams of high flame resistance made from chloral to mono- or preferably can be. This process variant is suitable for polyols, such as ethylene glycol, 1,4-butanediol or hexane, in particular for directing polyurethane foams irregular diol into completely open-celled products through the addition of 2 moles of chloral with an excessive pore structure. These addition products have a lower transfer rate with a regular pore structure. In the case of reactivity to than the free polyols, so that this process variant can be of advantage to achieve the greatly increased latency times when mixing the various inorganic-like systems containing water of crystallization with polyisocyanates and from compounds, water-soluble sodium silicates, sufficient time to load with the Carry out pre-selected trium aluminate or metal hydroxide or oxide mixtures. Here, during the phase to be used and then in the second phase, the iso-chloral reaction is partially set free again to carry out cyanate reactions, since high filler weights are obtained here, but bound by urea that is also used, and the fillers are also in. According to a similar principle, matrices can be laminated and fixed in an excellent manner and loaded with blocked amines or polyamines. become, such as B. bis-ketimines from 2 moles of cyclo-

It is also possible to use the polyurethane foam with 35 hexanone and 1 mole of hexamethylenediamine, or with

fabric matrices with other fillers, such as aluminum salts, z. B. of 2 moles of trichloroacetic acid to 1 mole

Silicates approximately of the gross formula AIjO ₃ 2SiO ₂ 2H ₂ O., Ethylenediamine, Hexamethylenediamine, Isophoronedi-

with a wide variety of silicas, optionally amine, isophoronediamine or m- or p-xylylenediamine.

in the presence of long-chain cation-active mono- or also the loading of the matrices with formic acids

To load polyamines and then the isocyanate reaction 40 salts of the aforementioned polyamines can often be advantageous

to run in the die. At this club.

By driving, it is also possible to use the most diverse In the most diverse process variants, the

Dye pigments or finely powdered metals, as can be used according to the invention, are in particular

Cu, Al or zinc, red phosphorus or sulfur, which the polyisocyanates react quickly with

various metal sulfides or metal sulfates in 45 preferred even in the presence of catalysts,

to laminate high concentrations in such a way that they are also coupled with polyaddition reactions

the foams are completely dust-free and one can completely deny it. There is a special procedure

even pore distribution and extremely high open- with the use of hydroxyesters

have cellularity. A wide variety of polyacrylic acid or methacrylic acid z. B. methacrylic

Siloxanes, which are also water donors, can contain acid-zS-hydroxypropyl esters, or hydroxy esters dei

optionally in the presence of silanetriols or maleic or fumaric acid alone or in the presence

are used, whereby open-celled, hydrophobicized from other vinyl monomers and radical formers

Foams are obtained. if telomerization or grafting reactions inner

According to another procedure, the half of the matrix are made according to the procedure of the deut

Foam matrices with high amounts of diol, e.g. 55 see patent application P1720 747.5 carried out

1,4-butylene glycol or 1,3-butanediol or 2,2-di- are supposed to be. Solutions de

1,3-methylpropanediol, loaded with a wide variety of high molecular weight synthetic poly

high amounts by weight that OH concentration in the meren, such as chlorinated rubber or in the isocyanate

There is an excess and a suitable butadiene polymer which is actually soluble by diisocyanate mixtures

polyaddition no high molecular weight products or copolymers, polyvinyl chloride, chlorine

should stand. Due to the regulating influence of rubber or polystyrene, polybutene oils, cellulose «

Phase interface and due to the fact that the aceiate, cellulose acetobutyrate, nitrocellulose, P0I3

The interface of a lamella always only contains small chlorobutadiene or other high polymers

Doses the reactant to the absorbing ddt, as well as highly chlorinated diphenyl od <

Releases isocyanate, 65 are perphenyl in this procedure.

Nevertheless, high molecular weight polyurethanes are obtained, which are particularly preferred when carrying out the "

the open-cell foam has a high tensile strength conversion of polyisocyanates with itself

speed ceben. It is also possible in the presence of the polyisocyanates or their mixtures ebc:

9 10

if the most varied of fillers, such as silicates, the When carrying out the Ver according to the invention

various types of silica, aluminum oxides, high amounts of heat can drive without shrinkage

Tin oxides, antimony trioxide, titanium dioxide, graphite, appearances of the resulting combination

Graphed coal, soot, a wide variety of inorganic foams can be discharged.

ganic and organic dye pigments, iron 5 A variant that is often used in acceleration

Oxide pigments, lead chromate, lead oxide or red lead generation of the reactions exist in the combination

are added, these mostly catalytically strong polymerization catalysts with inhibitors

act and accelerate the ongoing reactions such. B. dimethylcarbamic acid chloride, benzylchlo

gen. Likewise, it is possible to use the most varied of rid or acetyl chloride to achieve a defined latency period

Metal powder to produce the polyisocyanate mixtures or their io before the start of the polymerization

To add solutions, whereby a strong loading of the matrices also runs smoothly

Acceleration in the course of the reaction is recorded, and the reaction at a desired point in time

so z. B. when using aluminum, copper, can be triggered.

Zinc, magnesium, calcium, iron, selenium or the implementation of the Ver

Copper oxide powder. Sulphates or chlorides upstream are also easy to use. If the to react

The above-mentioned metals cannot be gaseous in high quantities of reactants to be brought with them

are used, furthermore red phosphorus, boric acids, both or one of the reactants should be countered

Alkali silicates, polyphosphoric acids, alkali aluminates, waiting of catalysts within the foam:

basic bismuth nitrate, heteropoly acids of Vana- are brought to reaction in ideal distribution

dins, tungsten or molybdenum, metal salts or ao The continuous technical implementation ge

Ganic carboxylic acids, as well as fillers, occur particularly in the case of an unpressurized version

Ganic origin, e.g. B. finely ground phenol of the process according to the invention simply because ii

Formaldehyde resins or urea-formaldehyde - the particularly preferred elastic foam

Condensates, as well as highly cross-linked melamine molding matrices, e.g. B. the density 20 to 35 kg / m ³

aldehyde condensates, or the most varied of an extraordinarily large volume of cell space for ver

known aging and ozone protection agents for poly-joining. This cell space volume is often in de

urethane. Such additives are able to add up to 800% of the die weight to fas

Reaction particularly well fixed and laminated. Also to bind any liquid reactants in this way

Silicates with limited or unlimited anions - that absorbed reactants are homogeneously ver

size shared by the most diverse cations, such as Mg, 30. Endless due to continuous loading

Na, Al, Ca, Mg or Fe, can be added, polyurethane tapes, by pressing and relaxation

can be laminated so that negatively charged high processes in suitable loading zones with suitable

molecular anions by positive metal ions in the roller devices that press the strip and into

Foam held together in good distribution can relax loading bath can therefore ii

will. Silanediols, higher molecular weight polymethyl- 35 depending on the void volume and in Ab

loxanes, silantnols can also be used depending on a subsequent z. B. mechanically he

^we i! ^the ·, “. . . , the following extrusion process by means of rollers almost every <

Another method variant consists in the arbitrary concentration of the reactants in de

Set the implementation of the matrix running under crosslinking. If desired, the poly

hydrogenating polyisocyanate polyadditions after the 40 urethane foam matrices only with one reaction

Procedure of the DT-OS 16 68 115. Here partners are loaded and in the second phase with the ge

the matrices with polyisocyanates and ζ B. equivalent reaction partners by gassing, Auf

valent amounts of nitro compounds loaded and let go of dissolved reactants, through Be

by means of reducing agents, the hydrogenating poly-spraying, dipping, etc. brought to implementation. Ii

In addition, the process according to the invention can trigger cross-linked high molecular weight 45 in many cases

Polyureas are created and rigid foams can be run at room temperature if necessary

Isocyanate releasers can, however, be obtained in temperature ranges from -30 to:

of various types, uretdione or carbodumide 160 ⁰ C are worked

group-containing polyisocyanates or their uretone- The process according to the invention can, however, also

itnindenvate can also be used. 5 »on foam sheets, on cellular moldings.

Since in the procedure according to the invention any kind, z. B. on cuboids, spheres, cylindrical.

Offenzell.gkeit the process products is retained, moldings, as well as small z. B. a cross

can be z. B following a foam with a cut of 0.5 to 2 cm

elasticizing reaction also further Modinz.erunpartikel z. B. in a fluidized bed

gen z. B to increase the hardness by performing 55, if desired with shaping

the modified matrix can be glued together as a new matrix for others

Reaction components are selected as foams, at their phase interfaces there

The process according to the invention can, however, also be carried out according to the invention

can be used for foam molding by adding the urethane groups and / or urea groups.

I. B on a die 60 located loosely in a mold and / or amide groups and / or isocyanurate groups.

High molecular weight polyisocyanate injected and foams containing open cellular NaWh

£ B open question after polymerisation has started. Polyurethane foams are preferred.

Plastics are obtained whereby it is often in a principle all polyurethane foams are un

Operation is possible, zones different depending on their type of manufacture and their segment

Produce elasticity and in particular cores or 6 _{5 structure can} be used. That means you can use the foam

to build up elastic zones, which are based on any polyhydroxy compounds like built-in high-material,

effective ted forces energy and vibration lying. It can be linear or branched polyethers

are devastatingly effective. _Polyesteri polycarbonate, polythioither polyacetals

primary, secondary or tertiary amino groups containing polyethers, polyester amides, polymerization or. Polyadducts of caprolactone with suitable ones Starters and mixtures of the types mentioned or urea, biuret, allophanate or isocyanurate groups containing foams can be used without in any way a Disturbance in the implementation of the method according to the invention would be recorded.

The particularly preferred polyhydroxy compounds forming the foam in the series of Polyesters are those made from polyhydric alcohols and predominantly aliphatic carboxylic acids, such as those in Technology can be used in all variations. The preferred polyols from the polyether series are those based on propylene oxide, ethylene oxide, their polyadducts with di- or higher-functional polyols, such as trimethylolpropane, glycerine, Sugar alcohols or pentaerythritol, their copolymerization products, e.g. B. with cyclohexene oxide, styrene oxide, Tetrahydrofuran, trioxane or cyclic acetates such as 1,3-dioxolane, ring acetals from di- or Triethylene glycol or thiodiglycol. Furthermore propoxylated or cyanoethylated mono- or polyamines, Polyketimines or aldimines, their hydroxymethylation or propoxylation products, as well as theirs With a deficit of polyisocyanates produced, only short-chain extended reaction products, as well as urethane groups and urea groups containing polyols.

The polyisocyanates bound in the foams can also be chosen as desired. In question come z. B. hexamethylene diisocyanate, m- or p-xylylene diisocyanate, 1,2-diisocyanatomethylcyclobutane, Isophorone diisocyanate or diuret polyisocyanates of these diisocyanates or urethane groups Polyisocyanates of these diisocyanates, also 1-methylbenzene-2,4-diisocyanate, l-methylbenzene ^ .o-diisocyanate, technical mixtures of these isomers, 4,4'-diisocyanatodiphenylmethane, its isomers or polynuclear aromatic polyisocyanates such as those used in the phosgenation of aniline-formaldehyde condensation products have been received. Also polyisocyanates, such as those produced by telomerization of any isocyanates with ethylenically unsaturated compounds according to the procedure of DT-OS 17 20 747 accessible can build up the polyurethane foam, as can liquid aliphatic polyisocyanates with semicarbazide groups, z. B. those from Ν, Ν-dimethylhydrazine and hexamethylene diisocyanate, as in the DT-OS 17 20 711 are described. Furthermore, the implementation of the invention Process used foams with a wide variety of natural or synthetic latices, Be impregnated with emulsions or dispersions of high polymers, e.g. B. with polyvinyl chloride, polyvinyl acetate, Ethylene vinyl chloride copolymers, polychlorobutadiene, natural rubber latex or Tar and optionally fillers and pigment colors.

The known catalysts are suitable, for. B. tert. Amines, phosphines, arsines, alkali salts of Phenols, of hexahydrotriazines, condensation products of phenols, formaldehyde and secondary Amines, if desired cocatalysts, e.g. B. from the series of epoxy compounds, can also be used. Benzoyl peroxide, butyl hydroperoxide, Di-tert. Butyl hydroperoxide or Λ, α'-azodiisobutyronitrile for use.

The process products are versatile due to their variably adjustable properties. It can e.g. B. highly elastic, natural rubber-like foams or semi-hard and very hard, but tough rigid foams can still be obtained. As shown in the examples, the inventive Process opened up unexpected possibilities for upgrading foams, whereby high increases in elasticity, elongation at break, strength can be achieved. The use of the new foams is therefore advantageous wherever there is increased elasticity, increased hardness, increased elongation at break Construction elements or increased resistance against hydrolysis, increased resistance to petrol and oil in the technical and construction sectors. Semi-rigid and rigid foams can also be used as excellent filter materials for removing solid particles

ao chen from liquids, as air filters for internal combustion engines or as excellent open-cell insulation materials for sound absorption and sound destruction.
A considerable technical advance also consists in the fact that one is able to produce a whole range of elastic or semi-rigid or rigid combination foams from flexible flexible foamsa, ie by selecting a single type of die, simply by means of the type and amount of suitable reaction components. By setting variable amounts of reactants, in the procedure according to the invention, foams with up to 85 percent by weight and more of open-cell fixed polymers can be produced on the basis of the same structure-imparting matrix type. Of course, a foam produced according to the invention, because of its open-cell nature, can in turn serve as a matrix for a different type of polyisocyanate modification, so that cell-shaped plastics can be obtained in an extraordinary variety by the process according to the invention.

The new process products can of course be further made up after their manufacture be, for example, by shaping, verpreßl, welded or diluted with ver Solutions of air-drying paints z. B. based on polyisocyanates and polyhydroxyl compounds or NCO one-component paints, furthermore with amines, polyamines or polyamidoareas curable polyepoxides or air-drying alkyd resins painted over by spraying, dipping or being layers. Furthermore, the combination foams can be used during or after their manufacture known flame retardants are added to reduce their flammability.

The parts listed in the examples are parts by weight unless otherwise stated

example 1

The elastic PoIj used in this example The urethane foam matrix was made in the following way:

100 parts by weight of a polypropylene glycol ether in its production trimethylolpropane and 1,2-Pr < Pylene glycol (1: 1) was used as a starter (OH number 47), 2.7 parts by weight of water, 0.8 weight parts of a silicone stabilizer, 0.1 parts by weight of PE

13 14

methylated diethylenetriamine and 0.23 parts by weight percent by weight of high molecular weight polyisocyanurate

a tin (II) salt of 2-ethylcaproic acid were copolymers of Example 1,

mixed together. _ · __ · _ ι ■> were added to this mixture

45.9 parts by weight of an isomer mixture consisting of bc ι s μ ι c ι j

from 80 parts by weight of 1-methylbenzene-2 _> 4-diisocyanate 5 The procedure is exactly as described in Example 1,

and 20 parts by weight of 1-methylbenzene-2,6-diisocyanate but uses polyurethane foams other than

added and with a high-speed stirrer well matrices, which were prepared as follows:

mixed. The white elastic foam was a) 100 parts by weight of a branched polyester

largely open-celled and had a density of diethylene glycol, trimethylolpropane and adipine

of about 35 kg / m ³ . i ° acid with OH number 62, 3 parts by weight of an accelerator

26 parts by weight of this matrix are in the form of nigers (adipic acid ester of N-diethylamine) and

a cuboid of dimensions 15 cm × 10 cm × 3.6 parts by weight of water are mixed. To this

5 cm (= 750 cm ³ ) soaked with carbon tetrachloride mixture are 42.5 parts by weight of an isomer

and squeezed. About 70 parts by weight are mixed - consisting of 80 parts by weight of 2,4-tons

Carbon tetrachloride with swelling of the matrix gel 15 luylene diisocyanate and 20 parts by weight 2,6-toluene

bound. The cuboid is then added with 120 weight diisocyanate and a high-speed one

share a Polyisücyanatlösung loaded, which mixes the fol- Rühier well. The foam has a

Low composition has: density of 43 kg / m ³ .

37 parts by weight of a diisocyanatopolyester, the b) 100 parts by weight of a branched propylene

from one mole of an adipic acid ethylene glycol 20 glycol polyether with an OH number of 56 (= trimethylolpro-

Polyester with OH number 56 and 2 mol 4,4'-diisopane as starter molecule), 4 parts by weight of water, 1 Ge

cyanatodiphenylmethane in a known manner, part by weight of a silicone stabilizer, 0.2 part by weight

was provided, 30 parts by weight of a low molecular weight dimethylbenzylamine as a catalyst and 0.27 Ge

Biuret polyisocyanates from 4,4'-diisocyanatodiphenyl parts by weight of a tin (II) salt of 2-ethylcapron-

methane, 30 parts by weight of 4,4'-diisocyanatodiphenyl acid are mixed with 46 parts by weight of the same poly

methane and 23 parts by weight carbon tetrachloride. isocyanate mixture, as described in Example 1, with

This solution is mixed with a high-speed stirrer for strong activation. Space weight

Isocyanurate polymerization 3.6 parts by weight Tris- 25 kg / m ³ .

(2,4,6-dimethylaminomethyl) phenol as a catalyst c) 100 parts by weight of a polythioether from thio

added. After adding the catalyst to the poly- 30 diglycol and triethylene glycol (70:30) with an OH number of 74,

isocyanate mixture remains a latency period of 3 to 3 parts by weight of the adipic acid ester of N-diethyl

5 minutes, during which the die is loaded with ethanolamine, 2 parts by weight of an emulsifier (oil-

will lead. The loading takes place in such a way that the acidic diethylamine), 1.5 parts by weight of water and

Squares pressed together and in the polyisocyanate 29 parts by weight of an isomer mixture, consisting

solution is relaxed. The interfacial reaction from 65 parts by weight of 2,4-toluene diisocyanate and

tion sets in after 2 to 3 minutes and is in 4 Mi- 35 parts by weight of 2,6-toluene diisocyanate, are with

utes finished. An open-cell combination stirrer is mixed with a high-speed stirrer. Volume weight

foam received. The primary swelling of the 73 kg / m ³ .

The matrix is changed by the rapid change in the aggregate 1,4-butanediol and formaldehyde (OH number 70) lated in the three dimensions of the space, resulting in a strongly grown, shrink-free cuboid, 2.5 parts by weight of dimethylbenzylamine, 0.2 parts by weight, which has the following dimensions: share tin (N) -dibutyl dilaurate , 2 parts by weight of oil - 11.4 cm x 5.6 cm 17.7 cm (= 1130 cm ³ ). There are 45 acidic diethylamine and 1.5 parts by weight of water compared to the matrix used, which acts as a structuring agent and 41 parts by weight of an isomer mixture, about 380 cm ³ in volume under 65 parts by weight of 2,4-toluene diisocyanai strong stress processes in the foam new and 35 parts by weight of 2,6-toluene diisocyanate, produced and quickly poly-converted through solidification. Density 68 kg / m ³ ,
merizing isocyanates irreversibly and shrinkage- 50 e) One uses an elastic polyurethane which has been freely fixed. A high-quality foam is obtained as a matrix, which consists of 100 parts by weight of rigid foam with a density of about 113 kg / m ³ , a bis-hydroxyalkylated butanediol-1,4-polycarbo with excellent properties, the open nates of OH number 63.1.5 Parts by weight of dimethyl cellity compared to the starting matrix is greatly increased by benzylamine, 0.2 parts by weight of tin (H) -dibutyldilau is. The combination foam consists of about 55 parts by weight of oleic diethylamine, 2.6 parts by weight of 79.5 parts by weight of polymerized, above-mentioned parts by weight of water and 43 parts by weight of one; ten biuret polyisocyanates. It is particularly suitable for sound isomer mixtures consisting of 80 parts by weight of insulation and for the production of industrial filters - 2,4-toluene diisocyanate and 20 parts by weight 2,6-To. luylene diisocyanate, and a room

B is ρ ie 1 2 ^{6o has a weight of 38 k} g / ^mS .

f) An elastic polyurethane is used

The procedure is as in Example 1, but used as a foam as a die, the 5 parts by weight of N-methylolcaprolactam catalyst specified in Example 1, ben produced with an increased amount of catalyst and containing 40 mg of potassium bound as alcoholate. however, in its preparation, hexamethylene diiso is accelerated the reaction by briefly 65 cyanate is used as the polyisocyanate. Room irradiation with an infrared lamp and receives at weight 42 kg / m ^s .

rapid polymerization is completely open g) An elastic polyurethane is used

cellular polyurethane foam, of which about 80 foam is used as a die, which is used as in Example 1

is produced, but in the production of which tri- (isocyanatohexyl) biuret, isophorone diisocyanate and m-xylylene diisocyanate are used in a ratio of 3: 1: 2. Volume weight 48 kg / m ³ .

h) A rigid polyurethane foam is used, the open-cell content of which has been increased by ^{mechanically producing about 80 cylindrical cells per cm 2 of} the film by vertical pressure with a needle-punched metal plate.

i) A rigid foam cuboid is used as a die, the polyol component of which was prepared from 1 mol of urea, 3 mol of formaldehyde, 0.5 mol of hexanetriol and 1 mol of tripropylene glycol according to the procedure of German Patent 10 49 094, has active N-methylol groups and contains 48 parts by weight an isomer mixture consisting of 80 parts by weight of 2,4-tolylene diisocyanate and 20 parts by weight of 2,6-tolylene diisocyanate, without the addition of water. By condensing the active N-methylol groups with themselves, water is supplied for the blowing reaction, as is the decarboxylation of the N-methylol urethanes. The rigid foam has a density of 68 kg / m ³ .

If the matrices are in the form of cuboids measuring 15 cm x 10 cm 5 cm as in Example 1 listed, loaded with the polyisocyanate mixture specified there, then after carrying out the Isocyanurate polymerization according to Example 1 is open-cell, excellent for air filters and for sound insulation get suitable elasticized rigid foams that are completely shrink-free and with exception of h) consist of about 74 percent by weight of three-dimensionally crosslinked polyisocyanurates, while at h) a modified rigid foam sheet is obtained which consists of about 44 percent by weight of polyisocyanurates consists.

Example 4

It is again the elastic polyurethane foam of Example 1 with the dimensions 15 cm χ 10 cm x 5 cm is used as a matrix, but it is loaded and the polyadding that is started afterwards Polymerization with the following components:

The matrix is first loaded with carbon tetrachloride clay. After 30 seconds, the swollen matrix is squeezed out so strongly that about 80 parts by weight of solvent remain in it, whereby it retains its swollen state. The amount of solvent fixed in the matrix contains about 0.6 parts by weight of a permethylated diethylenetriamine as a polymerization catalyst, which is evenly distributed in the foam. The matrix is then sucked in a solution of 40 parts by weight of an oxyethylated trimethylolpropane with an OH number of 570, 10 parts by weight of a polyester of adipic acid, phthalic acid and hexanetriol with an OH number of 370, 20 parts by weight of carbon tetrachloride and 65 parts by weight of a liquid polyisocyanate containing carbodiimide groups was obtained from 4,4'-diisocyanatodiphenylmethane by brief heating to 18O ⁰ C, loaded. After a few minutes, the polyaddition and trimerization of the isocyanatopolyurethanes that are formed is complete. A high-quality, open-cell rigid polyurethane foam is obtained without any signs of shrinkage, with a tensile strength of 2.8 kp / cm ² and an elongation at break of 55%. The combination foam contains about 80 percent by weight of newly formed polyurethane polyisocyanurates. The irreversible fixation of the new space created by the swelling is around 400 cm ³ , which is around 53 percent by volume based on the matrix used (^ 750 cm *}.

Example 5

The polyurethane foam blocks used in Example 1 the dimensions 15 cm X 10 cm X 5 cm are in a first phase each with solutions or Suspensions of the following reactants containing hydroxyl groups or amino groups in ethyl acetate loaded:

a) 9 parts by weight of 1,4-butylene glycol,

b) 11 parts by weight of hexanediol,

c) 5 parts by weight of Ν, Ν-dimethylhydrazine and
Hydrazine hydrate (2: 1),

d) 6 parts by weight of Ν, Ν-bishydroxyethylhydrazine,
e) 8 parts by weight of the formic acid salt

2 moles of formic acid and 1 mole of hexamethylenediamine,
g) 11 parts by weight of the liquid salt from 1 mole of imidazole and 1 mole of formic acid,
h) 17 parts by weight of adipic acid dihydrazide,

i) 15 parts by weight of a resol type containing methylol groups prepared from 1 mole of phenol and 5 moles of formaldehyde in the presence of trimethylhexahydrotriazine,
j) 3 parts by weight of ethanolamine,

k) 6 parts by weight of N-methyl diethanolamine,
1) 30 parts by weight of a bis-ketimine from 2 moles of cyclohexanone and 1 mole of hexamethylenediamine, m) 17 parts by weight of a cyclohexanone-formaldehyde resin from 1 mole of cyclohexanone and 3 moles of formaldehyde, which was prepared with trimethylhexahydrotriazine as a catalyst,
n) 7 parts by weight of trimethylol melamine and 2 parts by weight of dimethylol urea,
o) 8 parts by weight of an addition product

1 mole of caprolactone and 1 mole of hydrazine,
p) 12 parts by weight of bishydroxyäthyUertem hydroquinone.

All samples a) to p) are freed from the solvent in vacuo, dried and then with a mixture of 20 parts by weight of carbon tetrachloride and 27 parts by weight of liquid carbodiimide groups containing 4,4'-diisocyanatodiphe-

loaded nylmethane with an NCO content of 29.5% by absorbing the mixture into the matrix. the The polyisocyanate solution contains 0.5 parts by weight of tin dibutyl dilaurate and 1.2 parts by weight as a catalyst a polymerization catalyst consisting of

Tris (2,4,6-dimethylaminomethyl) phenol. The coupled polyaddition and polymerization set already one after one minute and be out in 3 minutes in a heat chamber at 90 ⁰ C to an end. Completely open-celled, stiffened and tough rigid foams are obtained which consist of high molecular weight, three-dimensionally crosslinked isocyanurate rings and polyureas, the proportion of which in the finished foam is between 57 and 68 percent by weight.

B e i s ρ i e 1 6

The cuboid used in Example 1 is with 3 parts by weight of triethylenetetramine, a weight

part of ethylamine and 5 parts by weight of a half-acetal from 1 mole of formaldehyde and 1 mole of methanol m 100 parts by weight of methanol soaked, with a higher molecular, basic hexahydroxy-containing mixed condensate forming in the matrix, which is an excellent polymerization catalyst. The matrix is then ^{dried at 50 °} C. in a vacuum. 27 parts by weight of a mixture consisting of 50 parts by weight of isomeric tolylene diisocyanates (2.4 to 2.6 parts such as 80:20), 50 parts by weight of ^ '- diisocyanatodiphenylmethane and 40 parts by weight of carbon tetrachloride are then sucked into the dry matrix. In a rapid and exothermic reaction, an open-cell rigid foam is obtained which has an elongation at break of 50% and a tensile strength of 1.8 kp / cm ² , with a density of 65 kg / m *. The open foam consists of about 51 percent by weight of crosslinked polyisocyanurates.

Example 7

The polyurethane foam quackers used in Example 1 and measuring 15 cm × 10 cm × 5 cm are each loaded with hexanediol by sucking in a solution of 11 parts by weight of hexanediol in ethyl alcohol. The Matnzen then dried in vacuo at 70 ⁰ C. Then the following polyisocyanate obtained by telomerization according to the procedure of DT-OS 17 20 747 for the polyadding polymerization in the Stvrol and 5 percent by weight of acrylonitrile gepiropk aryroi ethyl acetate and 1 part by weight

Swdrotriazine.

Substance atmosphere in a heating cabinet) JJ. _{Polyaddi e} rende polymerisation or with it ^^ "^ olymerisation or graft reaction ^ coupled ν my P> vacuum at 70 ° C

J ^ SK finished a few minutes. Man he led and * in we ^ g _{foams) dje offer} ,., _M

hau Mi ajo s> " _{Over 50 percent by weight}

i. ^^ _fi 3S, ^, _yiirethiUl .polyisocyanuraten entan moainz '£ _{ff; df reason their open} .

The hook * ™™ * ° ™ _{^S? 0Kastmktm especial} s as zelhgke, and the systems _{s and ak?}

LuMlter «y« ° ^separation
suitable filter.

Example 8

The following examples show improvements in the elasticity of Sutnita.

Tensile strength and elongation at break:

, 5 ^U ^ f _t ^he _E ^d _s ^ _gs soaked in external ethyl ester, squeezed out ^with / ^ ' ⁸ S JSSditsteile an about 50 "/ igen

and

Number out of a mole of one

-Polyesters (OH-y

30th

ry ^ holds one

by similar F'fropfreaktionen 30 weight percent meth _t ^ methyl acrylate and 10 weight percent styrene containing 64 percent by weight, together with 60 parts by weight 35 parts by weight of polyisocyanurates tri-n-butylphos- ^ J

^ TÄSSSÄ ^{and 1Ge} - ⁴⁰ »

c) 65 parts by weight of a modified m-xylylene weight of 90 kg / m

μ,

parts by weight tri- (isocyanatohexyl) -biuret, 0.4 weight- of an elasticity of

share azoisobuVyric acid dinitrile and 0.8 parts by weight 50 B e i s ρ i e 1 9

^ of an unsaturated polyester work exactly as described in Example 8,

harLf _a rAd! pinlLre, MaleLäureWhydrid, Di- uses the same rea ^ n components leads

ethylene glycol and hexanetriol, 15 parts by weight of styrene, but the loading of the matrix only with 48.8 parts

1 8 parts by weight of a 30% benzoyl peroxide paste, 55 parts by weight of the 50 ^ igen solution

0 SvichtSeätthylacetit ^g 40 parts by weight 4,4'-Di- Wttiend die Matnx ^^% isocyanatodiphenytoethane and 2 parts by weight tri-

f polyepoxide with sec.

Hydronli ™ pen (2.8% OH) from 4,4'-dihydroxydiphen ^ idime ^P thylmethan ° and epichlorohydrin, 55 parts by weight 4 ₁ 4'-diisocyanatodiphenylmethane, 20 parts by weight ethyl acetate and 1 part by weight trimethylhexahyclrotriazine.

g) 40 parts by weight of a linear diisocyanatopolyätlwi-s from 2 moles of 4,4'-diisocyanatodiphenylmefhr and one mole of a ^ co-dihydroxypolypropylene blend cer OH number 47, with 28 percent by weight of ^ Ä an elongation at break of 185% and an elasticity of 45%. The foam occupies a

Volume weight of 65 ^ _o ^. ^ ™ J ^ 48 percent by weight of high molecular weight polyurethane polyisocyanurates ^

Example 10

· · _N · · ι ο κ u · κ α

Proceed as described in Example 8 and

uses as matnx the bleach lP «l3j ^ ™ chaum-

type of substance, but in the form of cut particles

with a diameter of 15 mm and weight of 26.6 g. If the polymerization is then carried out in such a way that the matrix is stored loosely during the polymerization, loose, non-glued, eSastified polyurethane foam particles are obtained. If the polymerization is carried out in a mold and the primary total volume of the particles is reduced from 1000 to 440 cm ³ by applying slight pressure, an open-celled, compact, cylindrical foam is obtained, which has high elasticity and consists of about 64 percent by weight high molecular weight polyurethane -Polyisocyanurate.

Example 11

The procedure is as described in Example 8, but a Diisocyanatopofyester is used as the polyisocyanate component, that of one mole of an adipic acid-ethylene glycol polyester the OH number 56 and 1.164 mol 4,4'-diisocyanatodiphenylmethane and about 50% was dissolved in ethyl acetate. To the Loading of the cuboid was about 64.8 parts by weight of this solution, 0.9 parts by weight of dimethylbenzylamine and 0.2 parts by weight of trimethylhexahydrotriazine are used.

After a few minutes, an open-cell, highly elastic foam is obtained which has a density of 78 kg / m ³ and consists of about 55 percent by weight of high molecular weight polyurethane polyisocyanurates. While the matrix has a tensile strength of 0.9 kp / cm ² , an elasticity of 34% and an elongation at break of 130%, the new, highly elasticized foam has a tensile strength of 2 kp / cm *, a significantly increased elongation at break of 240% and an elasticity of 42%.

If, in this example, the diisocyanatopolyester is replaced by a diisocyanatopolyether, which is prepared in a known manner from one mole of a linear tetramethylene glycol polyether with an OH number of 56 or ethylene glycol polyether with an OH number of 76 and 1.164 moles of hexamethylene diisocyanate, after the crosslinking polymerization is carried out, at 100 ⁰ C in the presence of potassium formate as the catalyst, and elasticized hydrophylierte foams with maximum elasticity increases, whereby achieved in a fraction of about 60 weight percent of polyurethane-polyisocyanurates elasticities to about 46%.

If the same cuboids are used as matrices, however, they are first loaded with about 1.5 weight percent hexamethylenediamine and then brings the isocyanate mixture into the Capillary space of the matrix, depending on the degree of loading, about 15 to 82 percent by weight is obtained Polyurethane - polyurea - polyisocyanurate showers of high elasticity.

With an injection syringe parallel to the main surfaces of the cuboid in its center 32 parts by weight of the 50% diisocyanato adducts injected in the form of a square pattern, so obtained one foams with less elastic outer edge zones and highly elasticized centers, which in the Inside the matrix how spring forces are at work.

Example 12

The procedure described in Example 1 is followed, but a technical reaction component is used Polyisocyanate mixture consisting of phosgenation products of aniline-formaldehyde condensates and has an NCO content of about 32.5%. 29.9 parts by weight of this polyisocyanate are diluted with about 29 parts by weight of ethyl acetate and in it dissolves 4 parts by weight of N-methylolcaprolactam, which contains about 50 mg of potassium bound as alcoholate. The polymerization is after a few Minutes ended. A hard foam which is completely open-celled is excellent for

ίο is soundproof and suitable as an air or oil filter and consists of around 51 percent by weight of polyisocyanurates. It has a density of about 50 kg / m ³ and, as a rigid foam, has a high tensile strength of 1.3 kp / cm ² and a high elongation at break of about 50%, while conventional rigid polyurethane foams produced by blowing reactions are not open-celled and only very low Have tensile strength and elongation at break.

B e i s ρ i e 1 13

The catalyst used in Example 12 is replaced by 2.6 parts by weight of dimethylbenzylamine and used 80 parts by weight of the polyisocyanate used in Example 12 as the polyisocyanate mixture

and 20 parts by weight of a mixture of 1-methylbenzene-2,4-diisocyanate and 1-methylbenzene-2,6-diisocyanate (80:20) and 70 parts by weight of ethyl acetate. When the polymerization is carried out, a. newly created space of around 400 cm ³ irreversibly fixed. A completely open-cell rigid foam is obtained which consists of about 75 percent by weight of polyisocyanurate copolymers, has a density of 102 kg / m ³ and is still completely open-cell; Despite its hardness, it has an astonishingly high tensile strength of 1.7 kp / cm ² and an elongation at break of 40%. Due to its low swellability and uniform pore structure, the foam is particularly suitable as an air filter in air conditioning systems and as a filter material for gasoline hydrocarbons and petroleum.

Example 14

The procedure is as in Example 13 and the elastic polyurethane foam blocks mentioned in Example 1 are used. The dies are first loaded with the following components:

a) 10 parts by weight of a finely powdered titanium dioxide suspended in 60 parts by volume of water and 20 parts by volume of an aqueous, approximately 40% strength rubber latex.

b) 10 parts by weight of finely powdered silica, suspended in 60 parts by volume of water and 20 parts by weight of an aqueous, about 40% strength poly-2-chlorob'atadiene latex.

c) 10 parts by weight of a finely powdered aluminum oxide suspended in 60 parts by volume of water and 20 parts by weight of an aqueous, 40% strength latex made from acrylonitrile, styrene and butadiene copolymers.

d) 10 parts by weight of antimony trioxide suspended in 60 parts by volume of water and 20 parts by weight of an aqueous, approximately 42% strength poly-2-chlorobutadiene latex.

e) 10 parts by weight of barium sulfate, suspended in 60 parts by volume of water and 20 parts by weight of an aqueous, about 40% strength polydimethylsiloxane'.atex.

f) 10 parts by weight of finely powdered ammonium hydrogen phosphate, suspended in 60 parts by volume Methanol

g) 10 parts by weight of powdered ammonium hydrogen phosphate, suspended in 60 parts by volume of acetone, which contains 8 parts by weight of cellulose acetate dissolved

h) 10 parts by weight of antimony trioxide, suspended in 60 parts by volume of toluene, which is 8 parts by weight of a chlorinated rubber in dissolved form.

i) 10 parts by weight of polymethylene urea, 60 parts by volume an aqueous cationic polyurethane dispersion with a solids content of 40%.

15th

All matrices are dried at 60 ° C. in vacuo to remove the solvents. A technical polyisocyanate mixture of aniline-formaldehyde condensates with an NCO content of 32% is then used to load the preloaded matrices a °. In each case 29.9 parts by weight of this polyisocyanate mixture are diluted with 29 parts by weight of ethyl acetate and 4 parts by weight of N-methylolcaprolactam, which contains 40 mg of potassium as alcoholate, are dissolved therein. The polymerization soon sets in, and hard foams are obtained in which the fillers mentioned under a) to h) are fixed and laminated in a dust-free manner. They consist of about 40 percent by weight of crosslinked polyisocyanurates, about 13.3 percent by weight of fillers, have a density of about 53 to 55 kg / m ³ , a tensile strength of 1.7 to 2 kp / cm ^a and elongation at break of about 50%.

The proportion of fillers can be increased further if the polyisocyanate mixture mentioned with the Fillers is sucked in, especially with the additional or exclusive use of Copper powder, aluminum powder, zinc dust or iron powder greatly accelerate the isocyanate reaction he follows. This is done using matrices that are loaded with an anionic polyurethane dispersion are made from linear polyesters, hexamethylene diisocyanate, ethylene diamine and propane sultone was, when using 10 parts by weight of a diisocyanatourethane from 2 moles of hexa- methylene diisocyanate and one mole of 1,4-butanediol obtained highly elastic foams which are completely open-celled are.

Example 15

SO

The polyurethane foam described in Example 14 is used as the matrix. 26 parts by weight each of the foam are in the form of small, easily swirlable particles of the diameter about 6 to 8 mm loaded with the following reaction partners:

a) 15 parts by weight of hexamethylene diisocyanate.

b) 15 parts by weight of m-xylylene diisocyanate.

c) 15 parts by weight of isophorone diisocyanate.

d) 15 parts by weight of tris (isocyanatohexyl) biuret.

e) 15 parts by weight of 4,4'-diisocyanatodiphenylmethane and 2 parts by weight of higher molecular weight technical isomers.

f) 15 parts by weight of a diisocyanatopolyester from 2 moles of 1,5-naphthylene diisocyanate and one Mole of a linear polyester diol from adipic acid, hexanediol and neopeiityl glycol.

g) 18 parts by weight of an isocyanate releaser

2 moles of phenol and 1 mole of 1-methylbenzene-2,4-diisocyanate.

The particles loaded in this way are then gassed with superheaters, steam, traces of trimethylamine and parts by weight of gaseous ethylenediamine at HO ⁰ C in a fluidized bed, the polyaddition being completed at the phase interfaces of the matrix in a few minutes. Completely open-cell foams are obtained which consist of more than 36 percent by weight of dust-free fixed polyureas.

Example 16

The procedure is exactly as in Example 15 and the particles are loaded with the following reactants:

a) 10 parts by weight of an addition product of one mole of 1,4-butylene glycol and 1 mole of maleic anhydride, 4 parts by weight of styrene, 0.2 part by weight of benzoyl peroxide.

b) 8 parts by weight of an N-methylol group high molecular weight anionic aqueous polyurethane dispersion based on Polyesters, hexamethylene diisocyanate, ethylene diamine and propane sultone.

c) 8 parts by weight of a high molecular weight cationic aqueous containing N-methylol groups Polyurethane dispersion based on polyesters, hexamethylene diisocyanate, N-methyl diethanolamine and dimethyl sulfate.

d) 10 parts by weight of an equivalent eo-diaminopolypropylene oxide from average molecular weight 2000.

The non-impermeable particles are gassed in a conical tube with a vigorous stream of nitrogen (at 110 °) saturated with tetramethylene diisocyanate. After about 10 parts by weight of tetramethylene diisocyanate have been metered into the fluidized bed, the interfacial reaction on the cellular matrices is ended. Completely open-cell foams are obtained which, in the case of b) ₍ c) and d), are highly elastic and consist of about 43 percent by weight of crosslinked polyurethanes or polyureas.

Example 17

Proceed as in example 15, but carry out the loading of the matrix particles with the following polyisocyanates:

a) 15 parts by weight of a triisocyanatourethane

3 moles of 1-methylbenzene-2,4-diisocyanate and one mole of trimethylolpropane.

b) 15 parts by weight of a polyisocyanurate from 1-methylbenzene-2,4-diisocyanate with an NCO content of 18.5%.

c) 15 parts by weight of a mixture of 50 parts by weight of tris (isocyanatohexyl) isocyanurate and 50 parts by weight of a triazinone derivative of 2 moles of hexamethylene diisocyanate and one mole of CO ₈ .

d) 15 parts by weight of a diisocyanate containing simicarbazide groups from one mole of N ₁ N-dimethylhydrazine and two moles of hexamethylene diisocyanate.

e) 19 parts by weight of a splitter containing NCO groups from 1 mol of 1-methylbenzene-2,4-diisocyanate and 1 mole of tert. Butanol.

The loaded particles are then gassed with a strong stream of nitrogen containing traces of trimethylamine and saturated with ethylene diamine vapor at HO ⁰ C in a fluidized bed. After a few minutes, completely open-cell foam

substances that consist of about 36 percent by weight of dust-free fixed polyureas or polyurea-polyisocyanurates exist.

Test report

The polyurethane foam cuboid described in Example 1 the dimensions 15 cm 10 cm χ 5 cm is mixed with a solution of 12 parts by weight of the Tetraisocyanates

made from an adduct of

a) 4 moles of ethylene oxide

b) HIGH ₂ . .CH ₂ OH

CH ₂ OH

and 4 moles of hexamethylene diisocyanate, impregnated 40 weight parts of styrene and 3 parts by weight of azobisisobutyronitrile as a polymerization catalyst in 80 parts by weight of xylene and kept for 12 hours at 10O ⁰ C in a grinding beaker in the absence of oxygen and in the presence of a N ₂ stream. Unpolymerized styrene and xylene are then removed in vacuo at 80.degree. A hard, dry foam is obtained whose irreversibly fixed increase in volume is about 70 percent by volume, based on the initial volume, of the foam. The proportion of polystyrene bound by grafting and polymerization reactions in the foam obtained is about 40 percent by weight.

The product of the process shows increased hardness and open-cell content of the foam obtained. the The sectional area shows that the polymerization has also taken place completely in the core of the foam.

attempt

The polyurethane foam cuboid used in Example 1 with the dimensions 15 cm × 10 cm × 5 cm (= 26 ^{parts by weight = 750 cm 3} ) is mixed with a solution of 36 parts by weight of styrene and 20 parts by weight of the urethane-free tetraisocyanate

OCN

CH

NCO

NCO

NCO

y \

and 5 parts by weight of azobisisobutyronitrile as a radical loaded by impregnation and subsequently then heated in a grinding beaker under a nitrogen atmosphere using an infrared lamp as a heat source with simultaneous removal of the methylene chloride first at 70 ⁰ C, to 95 ° C. After 2 hours, the polymerizing graft and polyaddition reaction is practically complete. A portion of 10 parts by weight of non-polymerized styrene is removed in vacuo and a hard, open-cell combination foam (= 72 parts by weight) is obtained, which is greatly enlarged in its dimensions and has an irreversibly fixed increase in volume of Δ = + 380 cm ³ , based on the initial volume of the Matrix thus an irreversibly fixed increase in volume was reached before about 50 percent by volume, with about 46 parts by weight of the liquid reactive partners being converted into solids. This solid formation is decisive for the irreversible fixation of the swelling state and the found - + - Δ V of 380 cm ³ .

609 614/8!

Claims (2)

1 2 and effects such as preservation of open cells, Zeil patent claims. Multiplication and spatial growth with strong, even dimensional changes of a given 1. A method for modifying polyurethane benches Mairix and converting them into the desired foams by treatment with polyisocyanates, if highly elastic, natural rubber-like polyurethane compounds, characterized in that foams or such semi-hard or tough and that polyisocyanates are either combination foams that are hard with themselves. or having connections with responsive waits. The hydrogen atoms and / or ethylenically unavailable process products are therefore new.
Saturated compounds in the presence of catalysis. It has also been found that, in particular, elastic formers in the capillary spaces and on the phase and soft polyurethane foams, through solvate interfaces, result in largely open-cell urethanation of the soft and / or urea and / or isocyanurate groups that make up the foam the inventive Veraufweisenden foams, where the drive, optionally in the presence of organic amounts of polyisocyanates and optionally 15 solvents, experience strong dimensional changes in the compounds with reactive hydrogen three directions of space and that these atoms experience at least 15 percent by weight of the original directional changes of the matrices very resilient foam. rapid physical changes and molecular 2. The method according to claim 1, characterized marked enlargements of the selected reactants, for. B. draws that the implementation in the presence of 20 aggregate changes in the sense: (gaseous or whisper-tertiary Bases, alkali phenolates, hexahydro- sig -> high molecular weight, solid) are fixed irreversibly, triazines, tris-dimethylaminomethylphenol, tri- which increases the open-cell content of the foams butylphosphine, tributylarsine, sodium and potash and new space for those arising on the matrix reformate, benzoyl peroxide, «,« '- azodiisobutter reaction products is created. As a result, conservonitrile, if necessary in the presence of polyurethane epoxides while maintaining their open-cell structure, takes place as catalysts. Foams are made in which the weight The proportion of the die used is surprisingly small without the use of propellants. must be turned. The method according to the invention differs from all previously known methods according to In general, the invention relates to the modification to which this z. B. layer-By with any adhesives cellular polyurethane plastics through the form glued, welded together, pressed A wide variety of reactions with isocyanates, where or are painted. Such known method in these are carried out in such a way that the open cells do not change the polyurethane foam The ability of cellular polyurethanes is not only preserved in terms of its overall properties, nor do they have an effect but is even increased and especially strong cell-multiplying in any way, cell-opening, much-J-cell enlargements, d. H. a strong dimensional increase - the cells are often compactly sealed of predetermined cellular polyurethanes, glued or coated on the surface, tn takes place in the three dimensions of space, and the 40 The method according to the invention distinguishes ! Substances formed during this reaction may also differ in principle from the procedure Its weight is a multiple of the cellular dimension of German patent specification 9 57 294 and of Polyurethane, at whose phase interfaces the impregnation and coating of carrier «Jie reactions are carried out. This creates materials with polyisocyanates, the impregnation novel polyurethane foams. 45 of polyurethane foams with polyisocyanates It has been found that rapid polymer and the impregnation and modification of nation and copolymerization reactions of poly foams due to slow-acting cross-linking isocyanates as well as their polyaddition to connection reactions by means of relatively small amounts of gene with active hydrogen atoms in the capillary polyisocyanates according to the German Auslegeschrift clear and open-celled at the phase interfaces 50 12 24 033, from which the increase in the rigidity of Polyurethane foams for new foams with polyurethane foams according to the procedure-Völlig result in unexpected properties. way of the USA.-Patent 32 98 857 by long- If the experiment is carried out appropriately, slight further cross-linking of the the resulting polymeric compounds the predetermined foams and increasing their Given the cell structures of the matrix, the stiffness is extended with the help of small amounts of Polyiso cells the matrix cyanates in the three dimensions of space, as well as by known methods of veraus and as a result of the stresses that occur, the adhesive or foaming of small, closed locks opens Cells of the templates presented. The invented cellular polystyrene foam reel particles with dung therefore opens up a large number of new, open-ended polyisocyanates and polyhydroxy compounds in cellular polyurethane foams, whereby also poly- 60 presence of blowing agents according to the process urethane foams from so far practically no reference to the French patent specification H 17 086. The foamable polyisocyanates and active hydrogen - so far with small amounts of polyisocyanates through atoms containing compounds produced will lead to guided impregnations and gluing be able. especially not for cell formation and spatial Interface reactions within the meaning of the invention 65 growth of the matrix and, moreover, the teaching So far, polyurethane foams have been given that in made-up or impregnated named species has not yet become known. The amount of polyisocyanate used after foams property changes achievable with the invention are small, if possible not more than about 15