DE2719372A1 - PROCESS FOR THE PRODUCTION OF FILLER-REINFORCED POLYURETHANE ELASTOMERS - Google Patents

Description

Bayer Aktiengesellschaft 27 19372

Central area of patents, trademarks and licenses

5090 Leverkusen, Bayerwerk Sft-mo

Process for the production of filler-reinforced polyurethane elastomers

The present invention relates to a method for producing filler-containing polyurethane elastomers with improved Interaction between the filler and the polyurethane. The improvement is made more containing ion groups by the incorporation organic compounds in the polyurethane molecule.

It is often desirable for economic reasons to provide polyurethanes with larger amounts of fillers because the resulting reduction in price opens up new areas of application. For many applications, the increase in Density due to the filler is disadvantageous because the required weights or dimensions are no longer required can be complied with. In these cases, however, the filled polyurethane can be foamed, i.e. used of blowing agents in the manufacture of the plastic, can be adapted to the required conditions.

Polyurethanes containing fillers in foamed or solid form are known. So is the use of fillers

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for homogeneous polyurethanes, for example, described in JH Saunders and KC Frisch, "Polyurethanes, Chemistry and Technology" (1964), Part I., page 343 and Part II, page 69 ff., likewise in Bayer-Kunststofftaschenbuch, 3rd edition 1963, page 138, and in the leaflet from Bayer AG on ( ^R ) Desmoflex dated September 1, 1967. H. Gruber also reports on it in "Polyurethane coatings in road construction" (Kunststoffe im Bau, special issue 9; publisher: Straßenbau, Chemie, Technik; 1st quarter 1968; Verlag-GmbH Heidelberg).

The use of fillers such as inorganic carbonates and sulfates, PVC powder or wood flour brings with it a deterioration in many mechanical properties in the previously known processes. Compared With unfilled polyurethane systems, filled systems show, for example, a significantly reduced elasticity, greater brittleness, great tendency to break and often inadequate tear strength.

The invention is based on the problem of the above-described disadvantages of the known filler-containing polyurethane plastics to avoid and, moreover, to produce novel composites, which in particular have the advantage have better interaction between the filler and the polyurethane matrix.

This object is achieved according to the invention through the concomitant use of hydroxy-functional ones containing anionic groups Chain extenders solved in the production of the polyurethane.

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The advantageous one is explained without thereby limiting the scope of the present invention Effect of the presence of ionic groups in the chain extender and thus in the polyurethane presumably essentially by interactions between the ionic groups and the surfaces of the filler particles that have a beneficial effect on liability. This effect is particularly pronounced when you combine inorganic particles want to connect. Because the surfaces of such particles are almost never completely neutral, or most of the time are positively or negatively charged, are made using either ionically modified chain extenders direct ion bonds created or through the interaction of opposing charges between filler and polyurethane binders achieved extreme bond strengths that are on the order of heterolytic Dissociation energies are likely to lie.

But they also come with organic filler particles interaction forces mentioned, although perhaps to a lesser extent, to train, especially with organic ones Polymers, which in turn have polar or polarizable groups in some form, because they are enough already polarization and induction effects lead to noticeable interactions with the ionic group of the chain extender and thus to achieve improved adhesion properties. The adhesion between substrate and binding agent - and this should be emphasized here very clearly - is arguably the most decisive factor for quality of a composite material, improving the adhesion between the phases, better performance properties of the composite material are achieved.

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Surprisingly, it was found that these improvements in properties with the diols containing sulfonate and / or phosphonate groups described below can be achieved to a particularly high degree.

The present invention therefore relates to a process for the production of optionally foamed fillers Polyurethane elastomers

(a) at least 2 Zerewitinoff-active hydrogen atoms containing compounds with a molecular weight between 400 and 10,000, preferably 800 to 6000, particularly preferably 1000 to 4000,

(b) organic polyisocyanates, if appropriate

(c) chain extenders with a molecular weight between 32 and 400,

(d) 50 to 500, preferably 75 to 250 parts, based on 100 parts of polyurethane solids, of an inorganic or organic filler and optionally

(e) propellants, catalysts and other additives,

which is characterized in that as component (a) and / or (c) polyhydroxyl compounds which contain at least one sulfonate and / or phosphonate group are also used in such an amount that the polyurethane 1 to 10, preferably 3 to 8,

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particularly preferably 3.5 to 7 percent by weight of sulfonate and / or phosphonate groups per Contains 100 g of polyurethane solids.

The polyurethane formulation preferably contains 40-91% by weight of nonionic, higher molecular weight polyhydroxyl compounds, 1-10% by weight of nonionic chain extenders, 1 - 10% by weight of sulfonate or diols containing phosphonate groups and 7-40% by weight of polyisocyanates.

According to the invention, diols containing sulfonate or phosphonate groups are preferred which have a melting point below 120 ° C. The following compounds are preferred according to the invention:

Diols of the formula containing sulfonate groups

(1) H- (0-CH-CH _{2) n} -0- (A) -CH- _O (B) _p -0- (CHj-CH-O) _m -H

* ⁽ ™ 2> q *

so ₃ (-)

in which

A and B are identical or different divalent aliphatic Represent hydrocarbon radicals with 1 to 6 carbon atoms,

R stands for hydrogen, an aliphatic hydrocarbon radical with 1 to 4 carbon atoms or a phenyl radical,

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I 7 1 9 3

X 'denotes an alkali metal _{cation or an ammonium group which is optionally substituted by C 1} - CQ-alkyl radicals,

η and m for identical or different integers from 0 to 30, preferably from 0 to 3,

ο and ρ for O or 1 and

q stand for an integer from 0 to 2.

Preferred diols containing sulfonate groups of the general my formula (I) are those of the formulas

a) H- (OCH-CH-) - 0 - CH, - CH - CH ₀ -O- (CH ₉ -CH-O) -H R CH ₂ R

SO ^(} X

^S0 3 ^X (I a)

b) H- ( _{O-CH-CH 9} ) -0-CH ₀ -CH-CH ₀ -CH ₀ -O- (CH ₀ -CH-O) _7n -H

R so ₃ ⁽ -)

_b)

C) H- (O-CH-CH ₀ ) -0-CH-CH ₀ -O- (CH ₉ -CH-O) -H δ η ζ 2 m

I. ι ι R. CH ₂ R. ι CH ₂

(I C)

in which

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R represents hydrogen or a methyl group, η and m are identical or different numbers from 0 to

represent and
X has the meaning already mentioned.

As already mentioned, diols containing sulfonate groups which have a melting or softening point below 120 ° C. are particularly preferably used in the process according to the invention. In the case of η = m = 0 in the case of compounds of the formula (I), this requirement is met in particular when X ^{(+) stands} for a lithium cation or for an NH ₄ ⁽⁺⁾ ion. If sodium or potassium salts of the diols containing sulfonate groups are to be used, it is particularly advisable to use compounds of the formulas (I a), (I b) and (I c) in which η and m (on a statistical average) have a value of 0.8 to 2 have. Those representatives of the last-mentioned compounds in which R is a methyl radical are very particularly preferred.

The compounds (I a) are prepared in a simple manner by reacting optionally alkoxylated 2-methylene-propanediol- (1,3) with a bisulfite X®HSO® in an aqueous medium. For this purpose, the unsaturated diol is dissolved in water and mixed with an aqueous solution of bisulfite, which has previously been adjusted to a pH of 7.1 with dilute lye X OH. The reaction mixture is stirred at room temperature, at the same time the pH is increased to 7.0 by adding dilute sulfuric acid

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7.1 held. The reaction is over when the pH value remains constant. It is then acidified to pH 2 and the excess SC> 2 is driven out by stirring. It is then neutralized with dilute alkali X OH and evaporated to dryness. The diol containing sulfonate groups is then extracted with methanol. In this production process, bisulfites X HSO ₃ and bases X OH are preferably used, in which X is potassium, sodium, lithium or ammonium. The sulfonate diols obtained in this way are converted into those in which X is another component, for example a substituted ammonium group, is carried out in a simple manner by replacing the initially present cation X with a hydrogen ion by means of an ion exchanger and then neutralizing the free acid obtained in this way the desired base.

The compounds (I b) are prepared in an analogous manner by adding bisulfite to, if appropriate alkoxylated 2-butene diol- (1,4).

The compounds (I c) are prepared in an analogous manner by adding bisulfite to, if appropriate alkoxylated 1-butenediol- (3,4).

The addition of bisulfite to such unsaturated diols is described in detail in the German Offenlegungsschrift 24 17 664.

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-73

(2) Diols containing sulfonate groups in general formula

whereby

χ ¹

HO- (CH _{2) n} -N- (CH _{2) m} -0H (CH _{2) p}

(ID

an alkali metal cation or an ammonium group optionally substituted by Cj-C-Q-alkyl radicals represents /

η and m for the same or different numbers from 1-6

and
ρ stand for an integer from 1-4.

Preferably used in the process according to the invention are diols of the general groups containing sulfonate groups Formula (II) are:

a) those of the formula HO- (CH ₀ ) -N- (CH_) -OH

£ Xl ■ ^ J XH

CH ₂

so <"> x < ⁺ >

(II a)

whereby

X has the above meaning and η and m are identical or different numbers from 1-6, preferably 2-4, stand,

b) those of the formula HO- (CH ₂ ) _n ~ N- (CH ₂ ) _m -0H

(CH ₂ ) ₄

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,. _χ (+) has the meaning given above and η and m are identical or different numbers from 1-6, preferably 2-4.

The compounds (II a) are prepared in a simple manner by reacting diethanolamine (or the ethoxylation product of diethanolamine) with formaldehyde and then with a bisulfite (HSO ₃ X).

The preparation of the compounds occurs (II b) by (or its Äthoxylierungsprodukt) dropwise to a solution of one mole of diethanolamine in 500 ml of toluene, a solution of one mole of butanesultone in 200 ml toluene, subsequently stirring for 12 hours at 40 ⁰ C and then concentrated, dissolved in 500 ml of water and converted into salt with sodium hydroxide solution.
Mp = 143-145 ° C (for m = η = o).

3) Diols of the general formula containing sulfonate groups

HO-CH ₂ -CH-CH ₂ -ORO-CH ₂ -CH-CH ₂ -Oh

ι ι

NR ¹ NR ²

^ Vn < ^CH 2> m

so ₃ <-> x < ⁺ > so ₃ <-> x ⁽⁺ >

(III)

in which

an alkylene radical with 2-4 carbon atoms and / or a divalent aromatic or araliphatic one

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IS

Represents a radical with 6 to 15 carbon atoms,

X stands for an alkali metal cation or an ammonium group optionally substituted _{with C 1} -C _{1Q -alkyl groups,}

2
R and R stand for hydrogen and / or identical or different alkyl radicals with 1-6 carbon atoms and

η and m mean the same or different numbers from 1 to 6.

Preferred to be used in the process according to the invention Diols of the general formula (III) containing sulfonate groups are:

a) those of the formula

CH

NR ^{1 CH} 3 NR ² (III a)

(CH ₂ )

so ₃ ⁽ -> x ⁽⁺ >

whereby

2
R and R stand for hydrogen or identical or different alkyl radicals with 1 to 6 carbon atoms, in particular 1-2C atoms,

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X has the meaning given above and m and η for the same or different numbers of 1 to 6, especially 2-4;

b) those of the formula

HO-CH ₂ -CH-CH ₂ -O

I I

NR ¹ NR ²

(CH ₂ )

whereby

X, R and R have the meaning given above and m and η are identical or different numbers of 1 to 6, especially 2-4, stand.

c) those of the formula

HO-CH ₂ -CH-CH ₂ -O-CH ₂ - / ΟΛ -CHj -O-CHj -CH-CHj-OH

I I

NR ¹ NR ² (III C)

I I

(CH ₂ ) _n (CH ₂ ) _m

whereby

X ', R and R have the abovementioned meaning and m and η for the same or different numbers of 1 to 6, especially 2-4, stand.

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The compounds (lilac / b and c) are produced from the corresponding bisepoxides (reaction products of hydroxy-functional aromatics and araliphatics and epichlorohydrin or epibromohydrin) and e.g. 2-aminoethanesulfonate or 2-methylaminoethanesulfonate or 2-Butylaminoethanesulfonate in aqueous solution at 20-5O ° C.

4. Diols containing phosphonate groups in general formula

° OR

-CH ₂ -CH- (CH ₂ ) _n -P < ₍₊₎ (IV)

OX

OH in what

R represents a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms or a phenyl radical,

X ^{(+) stands} for an alkali metal ^{cation, in particular Na (+)} or K, or an ammonium group which is optionally substituted by Cj-CjQ-alkyl radicals and

η is an integer from 1 to 4.

Phosphonate group-containing diols of the above general types which are preferably to be used in the process according to the invention Formula are those in which n = 1 and R stands for hydrogen, methyl or ethyl.

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The preparation of the compounds (IV) takes place, for example, by adding 1 mol of a 75% phosphorous acid or dissolve their alkyl or phenyl esters in approx. 200 ml of water and add 1 mol in to this mixture at 0 to 10 ° C 75 ml of toluene dissolved glycide are added dropwise within 35 minutes. It will take 2 hours at 0-10 ° C and 2 1/2 Stirred for hours at room temperature. Then 1 mol of sodium hydroxide solution is added to 100 ml of water at 20-25 ° C dripped in. The organic phase is then separated off from the aqueous phase. From the aqueous phase the diols containing phosphonate groups to be used according to the invention are obtained as oily compounds.

The diols described above and preferred according to the invention generally have 60-700, preferably 200-600 milliequivalents of anionic groups per 100 g.

From the German Offenlegungsschrift 2 446 440 is the Described concomitant use of diols containing sulfonate groups in the preparation of aqueous polyurethane dispersions. However, this has to do with the process according to the invention for the production of optionally foamed polyurethane elastomers Nothing to do. Also through the incorporation of fillers into the ionically modified polyurethane Nothing is said in DOS 2 446 440.

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Any aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates can be used for the process according to the invention, such as those described, for example, in US Pat. B. by W. Siefken in Justus Liebifs Annalen der Chemie, 562, pages 75 to 136, are described, 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-S ^ S-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, American patent 3 401 190) , 2,4- and 2,6-hexahydrotoluylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or A _f 4-phenylene diisocyanate, perhydro-2,4 ¹ - and / or -4,4'- 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, triphenylmethane-4,4 ', 4 ^M -triisocyanate, polyphenyl-polymethylene-polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and, for example, in de n British patents 874 430 and 848 671 are described, m- and p-isocyanatophenylsulfonyl isocyanates according to the American patent 3 454 606, perchlorinated aryl polyisocyanates, as they are, for example, in the German Auslegeschrift 1 157 601 (American patent 3 277 138; are described, polyisocyanates containing carbodiimide groups, as described in German patent specification 1,092,007 (American patent specification 3,152,162) , diisocyanates as described in American patent specification 3,492,330, polyisocyanates containing allophanate groups, as described, for example, in British Pat Patent specification 994 890, the Belgian patent specification 761 626 and the published Dutch patent application 7 102 524 are described containing isocyanurate groups

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Polyisocyanates, such as are described, for example in the American patent specification 3,001,973, in German Patents 1,022,789, 1,222,067 and 1,027,394 and in German Offenlegungsschriften 1,929,034 and 2,004,048, polyisocyanates containing urethane groups as BB · are described in Belgian Patent 752,261 or in the aaerika African Patent 3,394,164, · Harnstoffgruppeη acylated containing polyisocyanates in accordance with the German Patent 1,230,778, polyisocyanates containing biuret groups, as described for example in German Patent 1101394 (American patents 3 124 605 and 3 201 372) as well as 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 specification 3,567,763 and in the German patent specification 1 23i 688, reaction products of the abovementioned isocyanates with acetals

and

according to German Patent 1,072,385, polymeric fatty acid residues containing polyisocyanates according to US Pat. No. 3,455,883.

It is also possible to use the distillation residues containing isocyanate groups and obtained during the industrial production of isocyanates, optionally dissolved in one or more of the abovementioned polyisocyanates. It is also possible to use any desired mixtures of the aforementioned polyisocyanates.

Particularly preferred isocyanates are polyphenyl polymethylene polyisocyanates with a functionality of 2.0 to 2.5, in particular 2 to 2.2, as produced by aniline-formaldehyde condensation and subsequent phosgenation can be produced.

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Starting components to be used according to the invention are also compounds having at least two isocyanate-reactive hydrogen atoms of one Molecular weight usually from 400-10 000. This includes amino groups, thiol groups or Compounds containing carboxyl groups, preferably polyhydroxy compounds, in particular two to eight Compounds containing hydroxyl groups, especially those with a molecular weight of 800 to 10,000, are preferred 1000 to 6000, e.g. at least two, usually 2 to 8, but preferably 2 to 4, hydroxyl groups Polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyester amides, such as those used for manufacture of homogeneous and of cellular polyurethanes are known per se.

The possible polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polybasic, preferably dibasic, carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to produce the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated.

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Mentioned as examples: succinic acid, adipic acid, azelaic acid, phthalic acid, trimellitic anhydride, phthalic anhydride, hexahydro phthalic anhydride, tetrachlorophthalic, Endo methylenetetrahydrophthalic, Glutarsäureanhy anhydride, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, acid dimethyl ester optionally in admixture with monomeric fatty acids, terephthalic acid and terephthalic acid-bis-glykolester. Examples of polyhydric alcohols include ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerine, trimethylol propane, hexanetriol- (1,2,6), butanetriol- (1,2,4) , Tri methylolethane, pentaerythritol, quinitol, mannitol and sorbitol, methyl glycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in question. The polyesters can have a proportion of terminal carboxyl groups. Polyesters made from lactones, for example t-caprolactone or hydroxycarboxylic acids, for example ω-hydroxycaproic acid, can also be used.

Also those that come into question according to the invention, at least two, usually two to eight, preferably two to three, hydroxyl-containing polyethers are such of the type known per se and are e.g.

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merization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of BF ,, or by adding these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or Amines, for example ethylene glycol, propylene glycol- (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers, as described, for example, in German Auslegeschriften 1,176,358 and 1,064,938, are also suitable according to the invention. In many cases those polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups present in the polyether) have primary OH groups. Modified by vinyl polyethers, such as for example, by polymerizing styrene and acrylonitrile in the presence of polyethers formed (US Patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German Patent 1,152,536) are also suitable, as well Polybutadienes containing OH groups.

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

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As polyacetals come e.g. those from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxäthoxydiphenyldimethyimethan, Hexanediol and formaldehyde preparable compounds in question. Also through polymerization cyclic acetals can be produced according to the invention suitable polyacetals.

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

The polyesteramides and polyamides include, for example, the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.

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

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Representatives of these compounds to be used according to the invention are, for example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", 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, for example on pages 45-71 .

It is of course possible to use mixtures of the above-mentioned compounds containing at least two isocyanate-reactive hydrogen atoms with a molecular weight of 400-10,000, for example mixtures of polyethers and polyesters.

Compounds with at least two isocyanate-reactive hydrogen atoms and having a molecular weight of 32-400 are also suitable as starting components to be optionally used according to the invention. In this case too, this is understood to mean hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl groups, preferably compounds containing hydroxyl groups and / or amino groups, which serve as chain extenders or crosslinking agents. These compounds generally have 2 to 8 isocyanate-reactive hydrogen atoms, preferably 2 or 3 reactive hydrogen atoms.

In this case, too, mixtures of different compounds having at least two isocyanate-reactive hydrogen atoms with one Molecular weights of 32-400 can be used.

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Examples of such compounds include: ethylene glycol, propylene glycol ( 1 , 2) and - (1,3), butylene glycol (1,4) and - (2,3), pentanediol ( 1 , 5), hexanediol - (1,6), octanediol- (1,8), neopentyl glycol, 1,4-bis hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerine, trimethylolprcpane, hexanetriol- (1,2,6), Tri methylolethane, pentaerythritol, quinitol, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, dihydric oil, 4 , 4- hydroxy-glycol, polybutylene glycol with a molecular weight of up to 400, castor oil, 4, 4-hydroxy diphenylpropane, di-hydroxymethyl-hydroquinone, 1, 4-phenylene bis (b-hydroxyethylether), ethanolamine, N-methylethanolamine,

Diethanolamine, N-methyldiethanolamine, triethanolamine, 3-amino propanol, ester diols of the general formulas

HO- (CH ₂ J _x -CO-O- (CH ₂ J-OH and

HO- (CH ₂ J _x -O-CO-R-CO-O- (CH ₂ J _x -OH
in which

R is an alkylene or arylene radical with 1-10, preferably

2-6, carbon atoms,
χ = 2 - 6 and

y = 3 - 5
mean,

e.g. cf-hydroxybutyl- 6-hydroxy-caproic acid ester, us -hydroxyhexyl- ^ -hydroxybutyric acid ester, adipic acid bis (/ $ - hydroxyethyl ester and terephthalic acid bis (ß-hydroxyethyl) ester!

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as well as diol urethanes of the general formula

HO- (CH ₀ ) -O-CO-NH-R • -NH-CO-O- (CH _P ) -OH in the

R 'is an alkylene, cycloalkylene or arylene radical 2-15, preferably 2-6, carbon atoms and

χ represent a number between 2 and 6,

for example 1,6-hexamethylene-bi3- (β-hydroxyethyl urethane) or 4,4'-diphenylmethane bis (J -hydroxybutyl urethane);

Diol ureas of the general formula HO- (CH ₉ ) -N-CO-NH-R "-NH-CO-N- (CH ₀ ) -OH

έ- X ι ι (L X

R "· R" ·

in the

R "is an alkylene, cycloalkylene or arylene radical with 2-15, preferably 2-9, carbon atoms,

R ^MI = H or CH ₃ and χ = 2 or 3

mean,

e.g. 4,4'-diphenylmethane bis - (ß-hydroxyethyl urea)

or the connection -, "

y ^H 3

HO-Ch ₂ -CH ₂ -NH-CO-NH- / \ " ^CH 3

CHCH ₂ -NH-Co-NH-CH ₂ -CH ₂ -OH

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Aliphatic diamines suitable according to the invention are, for example, ethylenediamine, 1,4-tetramethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine and mixtures thereof, 1-amino-3,3,5-trimethy1-5-aminomethylcyclohexane, 2,4- and 2,6-Hexahydrotoluylenediamine and mixtures thereof, perhydro-2,4 ¹ - and 4,4'-diaminodiphenylmethane, p-xylylenediamine, bis- (3-aminopropyl) -methylamine, etc. Also hydrazine and substituted hydrazines, eg methylhydraζin, Ν , Ν'-Dimethylhydrazine and its homologues and also acid dihydrazides are suitable according to the invention, for example carbodihydrazide, oxalic acid dihydrazide, the dihydrazides of malonic acid, succinic acid, glutaric acid, adipic acid, β-methy / adipic acid, sebacic acid, hydracrylic acid and terephthalic acid, e.g. ß-Semicarbazido-propionic acid hydrazide (DOS 1 770 591), semicarbazido-alkylenecarbazine esters such as, for example, 2-semicarbazidoethyl carbazine ester (DOS 1 918 504) or amino-semicarbazide compounds such as, for example, ß-aminoethyl-semicarbazide o-carbonate (DOS 1 902 931).

Examples of aromatic diamines are bisanthranilic acid esters according to German Offenlegungsschriften 2 040 644 and 2 160 590, 3,5- and 2,4-diaminobenzoic acid esters according to DOS 2 025 900, which are in German Offenlegungsschriften 1 803 635, 2 040 650 and 2160 589 described ester group-containing diamines, as well as 3,3 ^f -dichloro-4,4 ^f -diamino-diphenylmethane, tolylenediamine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl disulfide called.

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According to the invention, compounds such as i-mercapto-3-aminopropane, if appropriate, can also be used as chain extenders substituted amino acids, e.g. glycine, alanine, valine, serine and lysine as well as optionally substituted dicarboxylic acids, for example, succinic acid, adipic acid, phthalic acid, 4-hydroxyphthalic acid and 4-aminophthalic acid can be used.

Furthermore, compounds which are monofunctional with respect to isocyanates can also be used as so-called chain terminators in proportions of 0.01 to 10% by weight, based on the polyurethane solids. Such monofunctional compounds are, for example, monoamines such as butyl and dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, piperidine and cyclohexylamine, monoalcohols such as butanol, 2-ethylhexanol, octanol, dodecanol, the various amyl alcohols, cyclo »hexanol, ethylene glycol, etc.

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According to the invention, however, it is also possible to use polyhydroxy compounds are used in which high molecular weight polyadducts or polycondensates in finely dispersed or dissolved form are included. Such modified polyhydroxy compounds are obtained if Polyaddition reactions (e.g. conversions between polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g. between formaldehyde and phenols and / or amines) directly in situ in the above-mentioned compounds containing hydroxyl groups. Such procedures are for example in the German Auslegeschriften 1 168 and 1 260 142, as well as the German Offenlegungsschriften 2 324 134, 2 423 984, 2 512 385, 2 513 815, 2 550 796, 2,550,797, 2,550,833 and 2,550,862. However, it is also possible, according to US Pat. German Offenlegungsschrift 2,550,860 discloses a finished aqueous polymer dispersion with a polyhydroxyl compound to mix and then to remove the water from the mixture.

When using modified polyhydroxyl compounds of the type mentioned above as a starting component in the polyisocyanate polyaddition process in in many cases polyurethane plastics with significantly improved mechanical properties.

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Those to be used in the process according to the invention Inorganic and organic particulate materials should have a grain size of 0.01 µ to 1000 µ, preferably 0.1 u to 200 u.

A wide variety of solid inorganic or organic substances can be used as fillers, for example Dolomite, chalk, clay, asbestos, basic silicas, sand, talc, iron oxide, aluminum oxide and oxide hydrates, alkali silicates, zeolites, mixed silicates, calcium silicates, calcium sulfates, aluminosilicates, Cement, basalt wool, bronze or silicon dioxide powder, Polyvinyl chloride, polystyrene, polyethylene, polypropylene, polyacrylonitrile, polybutadiene, polyisoprene, polytetrafluoroethylene, aliphatic and aromatic polyesters, melamine urea or phenolic resins, polyacetal resins, Polyepoxides, polyhydantoins, polyureas, polyethers, polyurethanes, polyimides, polyamides, polysulfones, polycarbonates, of course, any copolymers as well. Foamed fillers can also be used according to the invention used, e.g. expanded clay or expanded polystyrene.

Particularly preferred materials are chalk, clay, asbestos, sand, calcium silicates, cements, lime, calcium sulfates, Aluminosilicates and barium sulfate.

According to the invention, water and / or volatile organic substances are used as propellants. Organic blowing agents include acetone, ethyl acetate, halogen-substituted alkanes such as methylene

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Chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, furthermore butane, hexane, heptane or diethyl ether in question. A propellant effect can also be achieved by adding compounds which decompose at temperatures above room temperature with the elimination of gases, for example nitrogen, for example azo compounds such as azoisobutyronitrile. Further examples of propellants and details of 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 described.

In order to control the time of the isocyanate reaction with isocyanate-reactive hydrogen atoms or else with other isocyanate groups in the desired sense / catalysts are often used according to the invention. 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'-dimethyIaminoäthyl-piperazin, Ν, Ν-dimethylbenzylamine, bis- (N, N-diethylaminoäthyU-adipat, Ν, Ν-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, Ν, Ν, Ν ', Ν ^1- tetramethyl-1,3-butanediamine, N, N-dimethy1-ß-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole, 2,3-dimethyl tetrahydropyrimidine, 2-aminopyrimidine, 2,6-diaminopyrimine and 2-hydrazinopyrimidine.

Tertiary amines containing hydrogen atoms active towards isocyanate groups are, for example, triethanolamine, triisopropanolamine , N-methyl-diethanolamine, 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.

Also suitable as catalysts are silaamines with carbon-silicon bonds, as described, for example, in German patent specification 1,229,290 (corresponding to American patent specification 3,620,984), for example 2,2,4-trimethyl-2-silamorpholine ^Un i.3-Diethylaminomethyl-tetramethyl-disiloxane.

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

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

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. Of course, in addition to the above-mentioned catalysts, mixtures can be used will.

Further representatives of catalysts to be used according to the invention and details about the mode of operation of the catalysts are given in the Kunststoff-Handbuch, Volume VII 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 on polyisocyanate, used.

As catalysts, which accelerate the reaction of the isocyanate groups with one another and thus, for example, the uretdione, Favor isocyanurate or carbodiimide formation, such as phospholine oxide, potassium acetate, hexahydrotriazine derivatives and pyridine derivatives are used.

These catalysts are also typically used in an amount between about 0.001 and 10% by weight, based on the amount on polyisocyanate, used.

According to the invention, surface-active additives such as

Emulsifiers and foam stabilizers can also be used. The sodium salts of castor oil sulfonates or malts of fatty acids are used as emulsifiers with amines such as oleic acid diethylamine or stearic acid diethanolamine are possible. Also alkali or ammonium salts of Sulphonic acids such as of dodecylbenzenesulphonic acid or dinaphthylmethanedisulphonic acid or of fatty acids such as Ricinoleic acid or polymeric fatty acids can also be used as surface-active additives.

Particularly suitable foam stabilizers are polyether siloxanes, especially water-soluble representatives. These compounds are generally structured in such a way that a copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane residue. Such foam stabilizers are described, for example, in American patents 2,834,748 , 2,917 and 3,629,308 .

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According to the invention, reaction retarders such as acidic substances such as hydrochloric acid or organic acid halides, 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, such as tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate, can also be used and polyphosphate, as well as stabilizers against aging and weathering influences, plasticizers and fungistatic and bacteriostatic substances

Further examples of surface-active additives and foam stabilizers as well as cell regulators, reaction retarders, which may be used according to the invention, Stabilizers, flame-retardant substances, plasticizers, dyes and fillers as well as fungistatiach and bacteriostatically active substances and details about the use and mode of action of these additives are in the Kunststoff-Handbuch, Volume VI, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on the Pages 103 to 113 described.

According to the invention is preferably carried out in the absence of water and in the absence of the usual organic solvents for polyurethanes such as toluene, ethyl acetate or DMF. The usual drying agents, preferably zeolites, can be added to render the reaction mixtures anhydrous will.

In general, in the manufacture of the polyurethane elastomers an index of 80-150, preferably 90-120, (equivalent ratio of isocyanate to hydroxyl and given

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if amino groups of about 0.8: 1 to 1.5: 1, preferably 0.9: 1 to 1.2: 1) are observed.

The manufacture of the composites can for example be as follows happen that in a batchwise or continuously operating mixing device, the described Components mixed with one another in one or more stages and the resulting mixture (mostly outside the mixing device) in molds or on suitable substrates.

Processing temperatures may vary between 10 ° C and 150 ° C, but preferably is the range between 20 ⁰ C and 110 ° C. A preferred procedure is that the components are combined at room temperature and then heated at 100 to 110 ° C within 10 minutes.

The mixture of components can also be cold or Pressing, pouring or injection molding heated molds and using these molds, be it relief or solid or hollow molds, if necessary, allow to cure by centrifugal casting at room temperature. The finished mixtures are used, for example, as coating materials for fabrics, e.g. for the backs of carpets, of polyvinyl chloride films or panels, both in foamed as well as non-foamed form application. The coating can be carried out using the following two methods:

1. The liquid to be coated is left on the liquid, knife-coated layer Material accumulates and leads the material with the mixture through a heating channel.

2. The reactive polyurethane mixture is placed in front of a Le A 17 994 - 32 -

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Doctor blade on the material to be coated.

In addition to carpet backing or PVC coatings, the filler-containing polyurethane mixtures according to the invention, containing sulfonate and / or phosphonate groups, can also be used for the production of foamed products with or without a homogeneous outer layer, for example shoe soles, as molded parts with a density of 0.2 to 1.0 g / cm, in particular 0.3 to 0.8 g / cm or as lightweight foam with a density of 0.01 to 0.2 g / cm, preferably 0.02 to 0.1 g / cm. _{Furthermore, the filler-containing polyurethane elastomers containing t} sulfonate and phosphonate groups according to the invention can also be used to produce seals (for example for air filters in motor vehicles or for clay pipes) , foils or tapes, for textile coating, for sound insulation or as coating compounds in construction.

The following examples explain the process according to the invention. To see whether the improvement in mechanical Values ultimately based on an emulsifier effect of the used Based on chain extenders containing sulfonic or phosphonic acid groups, this possible influence was initially indicated an unfilled system, which however represents the basis of the filled system, checked and with the basic approach compared. Comparative Examples A to E show that there is no such influence. In the comparative examples F to H and Example I was the possibility of an emulsifier effect of the ionically modified chain extenders checked in filled systems. The mechanical values give no indication of such an effect. For the purpose of those from Examples A to H provide an improved overview

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and Example I, the values obtained are also summarized in Table I.

The influence of the ionically modified chain extenders in filler-containing polyurethane elastomers on the mechanical properties is probably based on the ionic Interaction between the filler bound in the polyurethane matrix and the filler built into the polyurethane matrix ionic groups. The influence of the proportion of ionic elements in the filler-containing elastomer body give examples I and 1 to 10 again.

The improvement in the mechanical values of the test specimens (for example tensile strength or tear strength) when diols containing sulfonate or phosphonate groups are also used is surprising. When using chain extenders containing ion groups and chalk as filler, the tensile strength increases by approx. 30 - 60%, the tear strength by approx. 30 - 35%, the hardness by approx. 5 - 10%, while elongation at break and elasticity remain almost constant. In the case of the fillers Al (OH) ₃ and barite, the improvement in the values is not quite as pronounced, but it is still noticeable.

The error limit for the measured values given in the examples is +0.05 MPa for tensile strength, and for Tear strength + 0.1 KN / m.

An improvement in the mechanical values can also be achieved when using inorganic fillers in combination with diols containing ion groups.

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Example A (comparative example)

90 parts of a trifunctional polyether polyol with an OH number of 35 and a molecular weight of 4800 were prepared from trimethylolpropane, propylene oxide and ethylene oxide, 10 parts of dipropylene glycol, 31.6 parts of crude 4,4'-diisocyanatodiphenylmethane (NCO content = 31%), 3 parts of zeolite and 0.3 part of 2,3-dimethyltetrahydropyrimidine are mixed within 30 seconds (NCO / OH = 1.1) and the reacting mixture is placed in a preheated mold poured. After a tempering time of 10 minutes at 110 ° C., the elastomer body is removed from the mold. The following mechanical Values are obtained:

tensile strenght DIN DIN 53504 2.5 MPa Elongation at break DIN DIN 53504 184 % Tear resistance DIN 53515 5.0 KN / m Shore hardness A 53505 54 elasticity 53512 30% Example B (comparative example)

90 parts of the above-described polyether polyol, 9.35 parts of dipropylene glycol, 2 parts of a polypropylene glycol from Molecular weight 415 (OH number 270), 31.6 parts of the above diisocyanate (NCO: OH = 1.1), 3 parts of zeolite and 0.3 part of the above pyrimidine derivative are processed as in Example A. The following mechanical values are obtained:

Tensile strength DIN 53504 2.41 MPa

Elongation at break DIN 53504 139%

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DIN 53515 4.35 KN / m DIN 53505 53 DIN 53512 37

Tear resistance Shore hardness A elasticity

Example C (comparative example)

The approach for producing the elastomer body is the same as in Example B (NCO: OH = 1.1). That in example B Polyether polyol used with a molecular weight of 415 and an OH number of 270 is replaced by 2 parts of the sulfonated Diols

H- (O-Ch-CH ₂ ^ -O-CH ₂ -CH ₂ -CH-CH ₂ -O- (CH ₂ -CH-O) -H CH ₃ S0 ₃ ⁽ ~ ⁾ Na ⁽⁺⁾ CH ₃

replaced. The following mechanical values are obtained:

Tensile strength elongation at break
Tear strength Shore hardness A elasticity

Example D (comparative example)

The approach for producing the elastomer body is analogous to Example A (NCO: OH = 1.1). However, there will be 2 parts of one Emulsifier that does not have any in the sense of the isocyanate polyaddition reaction isocyanate-reactive hydrogen atoms (oleic acid oxyethane sulfonate) are also used.

DIN 53504 2.53 MPa DIN 53504 200% DIN 53515 5.1 KN / m DIN 53505 60 DIN 53512 31%

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The following values are obtained:

tensile strenght DIN 53504 DIN 53505 2.2 MPa i Elongation at break DIN 53504 DIN 53512 148 % Tear strength DIN 53515 Example E (comparative example) 4.0 KN / m Shore hardness A 56 elasticity 32 \

The approach to the production of the elastomer is analogous to Example D, but 2 parts of diethylaminooleate are used as Emulsifier used. The following mechanical values are obtained:

tensile strenght DIN 53504 DIN 53505 2.25 MPa Elongation at break DIN 53504 DIN 53512 119% Tear strength DIN 53515 Example F (comparative example) 5.2 KN / m Shore hardness A 70 elasticity 37%

The reaction mixture is analogous to Example A. However, 100 parts of chalk are used, the chalk being stirred evenly in the polyol mixture over a period of 15 minutes. Then 31.6 parts of the diisocyanate (NCO: OH = 1.1) are added. The mixture is stirred for 30 seconds at room temperature, poured out in a preheated mold, annealed 10 minutes at 110 ⁰ C and taken out of the elastomeric body from the mold. The following mechanical values are obtained:

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DIN 53504 2.44 MPa DIN 53504 1.10 % DIN 53515 6.35 KN / m DIN 53505 75 DIN 53512 22%

tensile strenght
Elongation at break
Tear propagation resistance
Shore hardness A
elasticity

Example G (comparative example)

Example D is made using 100 parts of chalk repeated (NCO: OH = 1.1). The following mechanical values are obtain:

tensile strenght DIN DIN 53504 2.16 MPa Elongation at break DIN DIN 53504 1.18% Tear resistance DIN 53515 6.2 KN / m Shore hardness A 53505 65 elasticity 53512 26% Example H (comparative example)

Example B is repeated using 100 parts of chalk (NCO: OH = 1.1). The following mechanical values will get:

tensile strenght DIN 53504 DIN 53505 2.3 MPa Elongation at break DIN 53504 DIN 53512 117% Tear resistance DIN 53515 Example I (according to the invention) 5.99 KN / m Shorte hardness A 75 elasticity 31%

Example C is made using 100 parts of chalk

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repeated (NCO: OH = 1.1). The following mechanical values will get:

Tensile strength DIN 53504 3.25 MPa

Elongation at break DIN 53504 105%

Tear propagation resistance DIN 53515 9.28 KN / m

Shorte hardness A DIN 53505 75

Elasticity DIN 53512 27%

Example 1 (comparative experiment)

Example F is repeated, replacing chalk with 100 parts of Al (OH) ₃ (NCOrOH = 1.1). The following mechanical values are obtained:

Tensile strength DIN 53504 2.28 MPa

Elongation at break DIN 53504 98%

Tear propagation resistance DIN 53515 6.67 KN / m

Shore hardness A DIN 53505 77

Elasticity DIN 53512 28%

Example 2 (according to the invention)

Example I is repeated, replacing chalk with 100 parts of Al (OH) ₃ (NCO: OH = 1.1). The following mechanical values are obtained:

tensile strenght DIN 53504 2.57 MPa Elongation at break DIN 53504 86% Tear propagation resistance DIN 53515 8.31 KN / m Shore hardness A DIN 53505 75 elasticity DIN 53512 26% Le A 17 994 - 39 -

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DIN 53504 2.48 MPa DIN 53504 90% DIN 53515 5.79 KN / m DIN 53505 75 DIN 53512 28%

Example 3 (comparative experiment)

Example F is repeated by replacing chalk with 100 parts of heavy spar (NCO: OH = 1.1). The following mechanical values are obtained:

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

Example 4 (according to the invention)

Example I is repeated, replacing the chalk with 100 parts of heavy spar (NCO: OH = 1.1). The following mechanical values are obtained:

Tensile strength Elongation at break Tear resistance Shorte hardness A Elasticity

Example 5 (according to the invention)

Example I is repeated with 5 parts of the diol containing sulfonate groups described in Example C and 8.38 parts of dipropylene glycol (NCO: OH = 1.1). The following mechanical values are obtained:

DIN 53504 2.85 MPa DIN 53504 93 % DIN 53515 7.78 KN / m DIN 53505 75 DIN 53512 26%

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DIN 53504 3.81 MPa DIN 53504 104% DIN 53515 10.79 KN / m DIN 53505 81 DIN 53512 27%

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

Example 6 (according to the invention)

Example I is prepared using 10 parts of the sulfonate grouped diol described in Example C and 6.75 parts of dipropylene glycol (NCO: OH = 1.1). The following mechanical values are obtained:

Tensile strength, elongation at break, tear resistance

Shore hardness A elasticity

Example 7 (according to the invention)

Example I is prepared using 1 part of the sulfonate group-containing diol listed in Example C and 9.67 parts of dipropylene glycol repeated (NCO: OH = 1.1). The following mechanical values are obtained:

DIN 53504 3.6 MPa DIN 53504 97% DIN 53515 9.38 N DIN 53505 86 DIN 53512 30%

tensile strenght DIN 53504 3.15 MPa Elongation at break DIN 53504 94% Tear propagation resistance DIN 53515 9.48 N Shore hardness A DIN 53505 80 elasticity DIN 53512 27%

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Example 8 (according to the invention)

Example 2 is made with 1 part of the sulfonate group-containing diol listed under Example C and 9.67 parts Dipropylene glycol repeated. The following mechanical values are obtained:

tensile strenght DIN 53504 DIN 53505 2.37 MPa Elongation at break DIN 53504 DIN 53512 90% Tear resistance DIN 53515 Example 9 (according to the invention) 7.79 KN / m Shore hardness A 75 elasticity 26%

Example 2 is with 5 parts of the sulfonate group-containing diol listed under Example C and 8.38 parts Dipropylene glycol repeated. The following values are obtained:

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

Example 10 (according to the invention)

Example 4 is prepared using 5 parts of the diol listed under Example C containing sulfonate groups and 8.38 parts of dipropylene glycol. The following values are obtained:

DIN 53504 3.25 MPa DIN 53504 85% DIN 53515 9.40 KN / m DIN 53505 81 DIN 53512 28%

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DIN 53504 3.49 MPa Ϊ KN / m DIN 53504 104 \ DIN 53515 9.59 DIN 53505 76 DIN 53512 26%

Tensile strength, elongation at break, tear resistance Shore hardness A elasticity

Example 11 (according to the invention)

90 parts of the trifunctional polyether polyol with the OH number 35 from Example A are mixed with 8.78 parts of dipropylene glycol and 2 parts of a diol containing sulfonate groups the formula

HO- (CH ₂ J _{2 (+) (} _j

HO- (CH ₂ J ₂ x> ^N " ^CH 2" ^SO 3 ^Na '

3 parts of zeolite, 0.3 part of 2,3-dimethyltetrahydropyrimidine and 100 parts of chalk are mixed well within 15 minutes at room temperature and then mixed with 31.6 parts of the diisocyanate described in Example A, stirred within 30 seconds and placed in a preheated mold given. After a tempering time of 10 min. At 110 ⁰ C of Gießllng is removed from the mold and tested for its mechanical properties. The following mechanical values are obtained:

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

DIN 53504 3.34 MPa DIN 53504 109 \ DIN 53515 9.67 KN / m DIN 53505 87 DIN 53512 26%

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Example 12 (according to the invention)

90 parts of the polyether polyol used in Example 11 were mixed with 8.98 parts of dipropylene glycol, 2 parts of one Diol containing sulfonate groups of the formula

HO- (CH ₂ ) 2 ^^,

'N- (CH ₂ ) ₄ -SO ₃ <

3 parts of zeolite, 0.3 part of the catalyst mentioned in Example 11 and 100 parts of chalk mixed and then mixed stirred with 31.6 parts of the diisocyanate used in Examples A to 12 within 30 seconds. Of the The casting obtained has the following mechanical values:

tensile strenght DIN 53504 DIN 53505 2.91 MPa Elongation at break DIN 53504 DIN 53512 124% Tear resistance DIN 53515 Example 13 (according to the invention) 8.82 KN / m Shore hardness A 84 elasticity 25%

Example 12 is made with 9.5 parts of dipropylene glycol and 2.5 parts of a bisulfonate of the formula

HO-CH ₂ -CH-CH ₂ -O - / ^ Vc / o \ o-CH ₂ -CH-CH ₂ -OH N-CH3 _CH3 ^N ~ ^CH 3 (CH _{2) 2} (CH _{2) 2}

repeated.

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The following mechanical values are obtained:

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

Example 14 (according to the invention)

Example 2 with 9.7 parts of dipropylene glycol and 2.5 parts of a diol of the formula containing two sulfonate groups

DIN 53504 3.79 MPa DIN 53504 114% DIN 53515 10.03 KN / m DIN 53505 89 DIN 53512 20%

HO-CH ₂ -CH-CH ₂ -O- (O> -O-CH ₂ -CH-CH ₂ -OH N-CH ₃ N-CH ₃

(CH ₂ )

repeated.

The following mechanical values are obtained:

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

DIN 53504 3.27 MPa k KN / m DIN 53504 129 \ DIN 53515 9.11 DIN 53505 84 DIN 53512 23%

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Example 15 (according to the invention)

Example 12 is made with 9.2 parts of dipropylene glycol and 2 parts of the diol containing a phosphonate group the formula

DIN 53504 2.87 MPa i KN / m DIN 53504 148 1 DIN 53515 7.41 DIN 53505 81 DIN 53512 24%

HO-CH ₂ -CH-CH ₂
OH

repeated.

The following mechanical values are obtained:

tensile strenght

Elongation at break

Tear propagation resistance

Shore hardness A

elasticity

Example 16 (comparative experiment)

82 parts of the trifunctional polyether polyol from Example A are mixed with 18 parts of dipropylene glycol, 30 parts of benzyl butyl phthalate, 0.5 parts of 2,3-dimethyltetrahydropyrimidine and 50 parts of PVC powder (grain size: 0.55, u) for 15 minutes at room temperature 64.3 parts of a reaction product of 4,4-diisocyanatodiphenylmethane with tripropylene glycol (NCO content: 23%) stirred within 30 seconds (NCO: OH = 1.1), the reacting mixture poured into a preheated mold, 10 min annealed 110 ⁰ C and demolded.

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DIN 53504 3.9 MPa DIN 53504 322 % DIN 53515 16.7 KN / m DIN 53505 84 DIN 53512 10%

The following mechanical values are obtained:

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

Example 17 (according to the invention)

Example 16 is made with 17.67 parts of dipropylene glycol and 1 part of the sulfonate groups used in Example C repeated chain extender (NC0: 0H = 1.1) The following mechanical values are obtained:

tensile strenght DIN 53504 DIN 53505 3.9 MPa Elongation at break DIN 53504 DIN 53512 205% Tear resistance DIN 53515 Example 18 (according to the invention) 20.8 KN / m Shore hardness A 83 elasticity 10%

Example 16 is made with 17 parts of dipropylene glycol and 3 parts of the chain extender containing ion groups from Example C repeated.

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

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DIN 53504 3.94 MPa I. KN / m DIN 53504 224 \ DIN 53515 23.8 DIN 53505 84 DIN 53512 11

Example 19 (according to the invention)

Example 16 is repeated with 16.3 parts of dipropylene glycol and 5 parts of the sulfonated diol:

tensile strenght DIN DIN 53504 4.60 MPa Elongation at break DIN DIN 53504 160% Tear resistance DIN 53515 27.8 KN / m Shore hardness A 53505 91 elasticity 53512 15% Example 20 (according to the invention)

Example 16 is repeated with 14.8 parts of dipropylene glycol and 10 parts of the sulfonated diol:

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

Example 21 (comparative experiment)

Example 16 is repeated using 50 parts of polystyrene powder as filler (grain size ^ 0.8, u (NCO / OH = 1.1). The following mechanical values are obtained:

DIN 53504 5.64 MPa I. KN / m DIN 53504 110 \ DIN 53515 28, 1 DIN 53505 94 DIN 53512 19%

tensile strenght DIN 53504 3.25 MPa Elongation at break DIN 53504 301 % Tear propagation resistance DIN 53515 14.72 KN / m Shore hardness A DIN 53505 83 elasticity DIN 53512 11 % Le A 17 994 - 48 -

809844/0510

27,9372 53

Example 22 (according to the invention)

Example 18 is repeated using 50 parts of polystyrene powder (NCO / OH = 1.1). The following mechanical Values are obtained:

Tensile strength Elongation at break Tear resistance Shore hardness A Elasticity

Example 23 (comparative experiment)

Example 16 is made using 50 parts of polyethylene powder as filler (grain size 0.5, u) repeated (NCO / OH = 1.1). The following values are obtained:

DIN 53504 3.67 MPa I. KN / m DIN 53504 234 \ DIN 53515 22.6 DIN 53505 84 DIN 53512 12%

tensile strenght DIN DIN 53504 3.84 MPa Elongation at break DIN DIN 53504 335% Tear resistance DIN 53515 14.22 KN / m Shore hardness A 53505 81 elasticity 53512 13% Example 24 (according to the invention)

Example 18 is repeated with 50 parts of polyethylene powder (NCO / OH = 1.1). The following mechanical values are obtained:

tensile strenght DIN 53504 4.01 MPa Elongation at break DIN 53504 232% Tear propagation resistance DIN 53505 21.5 KN / m Shore hardness A DIN 53505 82 elasticity DIN 53512 13th Le A 17 994 - 49 -

8098U / 0S10

Table I Overview table of the mechanical values of the

unfilled elastomers compared to filled.

example A. B. C. D. E. [F G H I. Share polyether
OH number = 35 90 90 90 90 90 90 90 90 90 Parts dipropylene
glycol 10 9.35 9.35 10 10 10 10 9.35 9.35 Parts of diisocyanate 31. 6 31.6 31, 6 31.6 31.6 31.6 31.6 31, 6 31.6 Share polyether
OH number = 270 - 2 - - - - - 2 - Parts ionic
modified diol - - 2 - - - - - 2 Parts oleic acid
oxyäthansulfona : - - - 2 - - 2 - - Parts diethyl
amino oleate - - - - 2 - - - - Parts 2,3-dimethyl
tetrahydropyrimi-
din
Share zeolite 0.3
3 0.3
3 0.3
3 0.3
3 0.3 '
3 0.3
3 0.3
3 0.3
3 0.3
3 Share chalk _ * _ 100 100 100 100 tensile strenght
(MPa) 2.5 2.41 2.53 2.2 2.25 2.44 2, 16 2.3 3.25 Elongation at break
(%) 184 139 200 148 119 110 118 117 105 Tear on
strength
(KN / m) 5.0 4.35 5.1 4.0 5.2 6, 35 6.2 5.99 9.28 Shore hardness A 54 53 60 56 70 75 65 75 75 Elasticity (%) 30th 37 31 32 37 Β 22nd 26th 31 27

Le A 17 994

809844 / 0S10

- 50 -

Table II

Mechanical values of filler-containing elastomers depending on the amount of ionically modified diol used

-IS-

fr66 Ll V

O σ co IO CO
* co O I. I. ■ "1 O
Ψ— * U. cn "■" ■ * O co I. 100 CM* I— « O
cn 9
ocT co in co
O* I. 3.49 104 σ
- 1 OO co
co co 100 I. in O
cn co
OO co t-H co
O* I. CM
co * in
OO CT) co co t-H co 100 I. O
cn Γ
ι «
cn CO co
*
O co , I. I. co
CM* O
OJ OO O
cn 9, 76 co O
ψ — t co
O* 100 3.15 cn r- in co
co co O
OJ CD* co m co
O* 100 co
co cn CO in - 4th
co CM co I. I. O
OJ co
00 * co I. co
O* co O
O I. 100 CO
co 104 in O
OJ 9.35 31. co
O* co I. 100 2.85 co
cn O
OJ O 31, 6 CM co
O* 2.48 O
cn co in 31.6 co O
O I. (^ O
OJ co
OJ * co I. co
O* I. O in
CM co
OO CM O O 31. co co I. OO
CM OO t-H cn co CM O* I. CM* OJ in co co I. I. in O
OJ co
OJ * co co
O* O
O CM
co * 105 · —I •-H
co

in
co
CO " t- CM
CM OJ cn * CO
t- co
CM O cn * r-i
OO OO 7.79 IO co
CM 9.48 O
CO t-
CM 9.38 co
OO O
CO P.
O*
_H CM CO r- * lO
t ~ CO
CM 5.79 t- OO
CM tH
CO
00 * in CO
CM C- ctf OO
CM co cn * in
r- t—
CM

U IT » O + J I. .-H I.
Q) C. Γ \ Φ CO IO ^^ tr » 4-1 < 4-1 Q) η «J ■ Η O + J • Η 4Y Ό ^^ α, (O C. • Η X! ■ Η C. Ό ■ Η , —Ι Ό 33 Ul Φ Qi V) I) CP IO O Q ■ Η , -η; Q) O M. • ε C. 4Y • Η x; C. ε χ; ε O Φ χ; Cn U N > 1 HJ Q) υ W. 4Y Q) φ ■ Η : ιθ ^ H -H O χ: Q) Q) U Xi 4Y Ό 4-1 ac 4Y O I. in υ 4-ϊ ε > 1 Φ υ • Η χ; Ul I. U) CU as a • Η Ul M. Q) rH φ ω Φ υ Φ O) O O • Η ■ Η Q) Q O - I ■ Η 3 rH Q) U α C. -, - Ι I. ■ Η Φ • rH φ CP M. CQ O ω QJ r-f CU ο N η • σ Q) φ f-H • Η CQ • Η χ; 1-I H -r-l Q) ■ Η Eh • rH 4Y Φ CO Q) Q) Q !-H Uh * (N χ! Φ ιη U •H Eh • Η Q) «J Eh φ U - P ₁ O) Q) r-H Q) M. UH φ ε Ul r- ( Eh ■ Η , —F 4-1 CP •H ■ H QJ • Η • Η ^ Q) Q) Eh Q) bsi Φ Ui CQ Eh Eh S -

Claims (8)

Claims 1) A process for the production of optionally foamed overall ¹ ^, filler-containing polyurethane elastomers from a) at least 2 Zerewitinoff-active hydrogen atoms containing compounds with a molecular weight of up to 10,000, b) organic polyisocyanates, if appropriate c) chain extenders with a molecular weight between 32 and 400, d) 50 to 500 parts, based on 100 parts of polyurethane solids, of an organic or inorganic one Filler as well as optionally e) Propellants, catalysts and other auxiliaries and Additives, characterized, that as component (a) or (c) having at least one sulfonate and / or phosphonate group Polyhydroxy compounds are used in such an amount that the polyurethane elastomer 1 to 10 percent by weight of sulfonate and / or phosphonate groups per 100 g of polyurethane solids contains. 2) Method according to claim 1), characterized in that the sulfonate groups containing polyols are those of Le A 17 994 - 52 - 809844/0510 2 7 19 general formula R H H- (0-CH-CH ₂ -) - 0- (A) _o -C- (B) -O- (CH ₂ -CH-O) -H ? 2q so ₃ (-) x ⁽⁺ ) are used, where A and B are identical or different divalent aliphatic hydrocarbon radicals with 1 to 6 Represent carbon atoms, R stands for hydrogen, an aliphatic hydrocarbon radical with 1 to 4 carbon atoms or a phenyl radical stands, X is an alkali metal cation or an optionally substituted one Ammonium group means η and m for identical or different numbers from 0 up to 30, ο and ρ for 0 or 1 and
q stand for an integer from 0 to 2. 3. The method according to claim 1, characterized in that polyols containing sulfonate groups are those the general formula HO- (CH ₉ ) -N- (CH ₀ ) -OH
fc η ι ^ XTi (CH ₂ ) _p can be used, where Le A 17 994 - 53 - 809844/0510 represents an alkali metal cation or an optionally substituted ammonium group and η and m stand for the same or different numbers from 1-6 and ρ stands for an integer from 1 to 4. 4. The method according to claim 1), characterized in that polyols containing sulfonate groups are those of general formula H 1 H 2 > η > m HO-CH - C-CH - ORO-CH
ζ, ζ <-> _χ < ₊ > 2-C-CH ₂ -OH M _x I ₊ ) NO NO
I. (CH ₂ (CH ₂ so ₃ I.
so ₃ can be used, where R is an alkylene radical with 2-4 carbon atoms and / or a divalent aromatic or araliphatic one
Represents a radical with 6 to 15 carbon atoms, X for an alkali metal cation or an optionally substituted one Ammonium group, 1 2 R and R for hydrogen and / or the same or different Alkyl radicals having 1 to 6 carbon atoms and m and η are identical or different numbers from 1 to 6 mean. 5. The method according to claim 1), characterized in that polyols containing phosphonate groups are those the general formula Le A 17 994 - 54 - 809844/0510 " - OR HO-CH ₂ -CH- (CHJP CT OH can be used, where R represents a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms or a phenyl radical, X for an alkali metal cation or an optionally substituted one Ammonium group stands and η is an integer from 1 to 4. 6. The method according to claim 1 to 5, characterized in that the sulfonate or phosphonate groups used containing polyhydroxy compounds 60-700 milliequivalents / 100 have g of anionic groups. 7. The method according to claim 1 to 6, characterized in that fillers having a particle diameter from 0.01 u to 1000 u can be used. 8. The method according to claim 1 to 7, characterized in that CaCO--, BaSO, - or Al (OH) ₃ ~ powder and / or PVC, polyethylene or polystyrene granules are used as filler components. Le A 17 994 - 55 - 809844/0510