DE2040650A1 - New aromatic diamines, a process for their production and their use for the production of polyurethanes - Google Patents

Description

- 2040650 FARBENFABRIKEN BAYER AG

GM / Bn

V ^ Patent Department

H Aug 1970

New aromatic diamines, a process for their production and their use for the production of polyurethanes

The compounds according to the invention are new chain extenders for the construction of plastics according to the diisocyanate polyaddition process. They influence both the processing and the mechanical properties of the plastics obtained and therefore occupy a special position among the previously known extension ~ average in.

As an extender for the construction of elastic polyurethane plastics e.g. aromatic diamines such as 4,4'-diamino ~ 3,3'-dichloro-diphenylraethane applied. These amines carry a chlorine atom in the o-position to the amino group, which the reactivity of the aromatic amino group towards the isocyanate group is reduced, so that good production conditions (e.g. sufficient pouring time) when processing in the liquid phase or when foaming are.

The present invention relates to aromatic diamines of the general formula containing ester groups

Ie A 15 169 - 1 -

109839 / H ₈₂

ROOC, R " Γ ¹¹ H ₂ N- ) -C-i R " Is
zJ C. COO-R ¹
/ > -NH ₂

in the

R and R ^{1 are} identical or different and are C _{1 -C 18} -i

preferably C ₃ -Cg -alkyl radicals, C ₄ -C ₁₄ -CyCXoalkyl radicals or Cg-C ₁ ^, - aryl radicals,

R "and R" · are identical or different and are hydrogen R "or Cj-Cg-alkyl radicals or

C ₄ -C 6 cycloalkylene radicals are represented.

The surprising observation was made that the ester group located in o-position to the amino group in the compounds according to the invention, the reactivity of the amino group towards isocyanates so greatly reduced that, as kinetic measurements show that the new compounds occupy an intermediate position in terms of their reactivity between the aliphatic glycols previously used on the one hand as an extension agent and those already mentioned on the other o-chlorine substituted aromatic diamines. That means, that the o-position ester group reduces the reactivity of the amino group much more than an o-position chlorine atom.

The compounds according to the invention are therefore eminently suitable for the construction of polyurethane plastics by a still more convenient processing due to a significantly longer casting time with an above-average short setting time,

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209839/1 182 or.g.nal inspected

which enables the cast plastics to be quickly removed from the mold. This fact provides the prerequisite for improved technical processing.

The compounds according to the invention, when used as chain extenders in the production of polyurethane elastomers, lead to plastics with high
Elasticity. The elasticity properties are dependent on the nature of the radicals R and R ¹ , in such a way that, with increasing chain length of the radicals R and R ^{f, more} elastic products are obtained. ·

Examples of compounds according to the invention are:

HC-CH ₂ OC,

^H 2 ^N ~ \ J / "

0 CH,

CO-CH ₂ -CH

^ CH,

"\ 3 ~ ^NH 2

CO-OC ₁₈ H ₃₇

0, H ₇ -O-CO C ^ H TT_N - // VS-i!

^C 6 ^H 13

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COO-C ₃ H ₇

-NH,

C ₄ H ₉ -O-CO

COO-C ₄ H,

H ₂ N-

-TXV- / " ^NH 2

C ₈ H ₁₇ -O-CO

CH,

C-

CO-OC ₈ H ₁₇

CH ₅

C ₆ H ₁₃ -O-CQ

C ₄ H ₉

- // W NH.

CH ₃
! ^ HC-CH ₉ -OC

CH ₃

CH

-C-CH

0 0-0CH ₂ -CH

/ ^CH 3

'CH,

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2Q4065Q

CH

C ₂ H ₅

0 η

-CH

C ₂ H ₅

The new connection can be established in the following way: '

Isatoic anhydride is first used with 'hydroxyl compounds of the formula R-OH
in the

R 0, -C ₁ Q-, preferably C, -Cg-alkyl radicals, C, -C. Means, -cycloalkyl radicals or CV-Cj, -aryl radicals in the presence of alkaline catalysts such as sodium hydroxide or tertiary amines such as triethylamine to form compounds of the formula

--COO-R -NH ₂

implemented. In the same way, by reacting isatoic anhydride with hydroxyl ^{compounds of the formula R'-OH, in which R 1 can have} the same meaning as R, compounds of the formula are obtained

One mole of each of these o-aminobenzoic acid esters can be used, for example, with

one mole of an aldehyde or ketone of the formula Λ

in the

R "and R" · are identical or different and are hydrogen or Cj-Cg-alkyl radicals or in the

C.-Cg-Cycloalkylenreet © mean

condensed, and the obtained condensation product is by the action of acids, preferably mineral acids such as

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') Π tl t / ' ι (l I '\ Λ Q') £ UJOJ ) / IIO Z

204Ö650

Hydrochloric acid, rearranged, resulting in the compounds according to the invention. The rearrangement usually takes place at temperatures of 40-130 ^° C., preferably between 50 and 100 ^° C., and can be carried out immediately after the condensation.

As aldehydes and ketones of the above general formula which are condensed with the o-aminobenzoic acid esters, there are in principle any suitable ones, such as formaldehyde, acetaldehyde, butyraldehyde, acetone, diethyl ketone, dibutyl ketone, cyclohexanone, cyclopentanone. Formaldehyde and acetone are preferred. The release of the process products from the reaction mixture after the rearrangement takes place, for example, through the action of bases such as aqueous ammonia solution. The products of the process are then isolated using catfish known per se.

The preparation of the compounds of the invention may be illustrated with 4,4 '~ Diamino-dipheny methane 3.3 ^t -diisobutyldicarbonsäureeaters explained!:

386.24 (2 mol) isobutyl anthranilic acid (boiling point at 1.7 mm Hg 135 ° C.) in 500 ml of ethanol are combined with 150 ml of 40 # formalin solution with stirring. The mixture is then heated to 60 ° C. for half an hour, diluted with 1 liter of water and the organic phase is separated off in a separating funnel. The aqueous phase is extracted by shaking with 200 ml of diethyl ether and, after combining with the organic phase that has already been separated off, evaporated on a rotary evaporator. The evaporation residue, which has a strong blue fluorescence, is dissolved in 700 ml of dioxane and poured into 700 ml of conc. Added hydrochloric acid at 50 ° C., the hydrochloride of 4,4'-diamino ~ diphe η ylmethane-313'-diisobutyl dicarboxylic acid ester being precipitated towards the end. After neutralization with ammonia solution, a reddish oil remains which solidifies anhydrous at room temperature. 356 g = £ 89 of that .

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BATH ORIGINAL

The substance can be identified after dissolving it in Deutero chloroform by NMR spectroscopy:

12 methyl protons attached, 1PPM

2 protons am $ ert. Carbon atom "at 2.1 PPM 2 CH ₂ protons at 4.0 PPM

4 OGHg protons at 4.2 PPM

4 HH ₂ protons at 6.2, PPM

as well as a sum of 6 aromatic protons.

The present invention is therefore also a Process for the preparation of aromatic diamines having ester groups of the general formula

in the

R and R ^{1 are} identical or different and C, -C ^ q-, preferably C ^ -Cg -alkyl radicals, C.-C ^. -Cycloalkyl radicals or CC /. -Aryl radicals,

R "and R ¹ " are identical or different and are hydrogen

or C, -C _< --- alkyl radicals or R " ^1-6

f -C- ■

CC-cycloalkylene compounds

^ ₆ ,

characterized in that compounds of the formula

COO-R

NH ₂

^{Le A 1} ^ ¹⁶ 9 20983-97Π82

in the

R and R ^{1 are} identical or different and are C ^ -C. · «-, preferably C ^ -Cg-alkyl radicals, .C ^ -C _1. -Cycloalkyl radicals or C ^ -C _1. -Aryl radicals

with aldehydes or ketones of the formula

R "»

in the

R "and R" 'are identical or different and are hydrogen

or C.-C _r -alkyl radicals or R " ^ b ^J

C ^ -C ^ -Cycloalkylenreete d employ,

condensed and the condensation product rearranged by the action of acids at 40-130 ^{0 C.}

As already described, the compounds according to the invention are valuable reaction components in the preparation of polyurethane plastics, especially polyurethane elastomers, although they are basically used to manufacture all types of polyurethane plastics, including foams, are suitable.

The present invention therefore also relates to a process for the production of optionally cell-shaped urethane groups containing plastics made from polyisocyanates, higher molecular weight Compounds containing active hydrogen atoms, aromatic Diamines, optionally water and / or other blowing agents, catalysts, emulsifiers and auxiliaries, characterized in that that as aromatic diamines compounds of the general formula

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nf \ r \ n ι

ROOC

in the

R and R ^{1 are} identical or different and are C ₁ -C ₁₈ , preferably Cj-Cg-alkyl radicals, C ^ -C ₁ , cycloalkyl radicals or Cg-C. , -Aryl residues,

R "and R" 'are identical or different and are hydrogen or Cj-Cg-alkyl radicals or

-R-

R "'

Represent C ^ Cg-Cycloalkylenreste,

be used.

The production of plastics from the inventive Connections are carried out according to methods known per se Reaction with higher molecular weight compounds containing isocyanate-reactive end groups and polyisocyanates. One can proceed in such a way that one first uses the higher molecular weight Reacts compounds with an excess of polyisocyanate, then adding the chain extenders according to the invention and the mixture in the presence or absence of any brings gas-releasing substance to reaction.

Another possibility consists in mixing the compounds according to the invention with the higher molecular weight compounds and then carrying out the reaction with isocyanates. The reaction of the new extenders with polyisocyanates can be carried out using all additives known in polyisocyanate chemistry, such as, for example, catalysts, gas releasers, ilainin-inhibiting substances.

Higher molecular weight compounds which are suitable for the present process are above all the higher molecular weight compounds Hydroxy compounds named, for example: Polyhydroxy compounds with a molecular weight of 750 to 10,000 of the conventional type, for example linear or slightly branched polyesters with terminal hydroxyl groups, such as they, for example, from mono- or polyfunctional alcohols and carboxylic acids or oxycarboxylic acids, optionally with use of amino alcohols, diamines, oxyamines and D! amino alcohols, are prepared by known processes can. Particular mention should also be made of the polyesters aliphatic polycarbonates wL e hexanediol polycarbonate and those produced by polymerization of caprolactone in the presence of starter molecules caprolactone polyester available such as glycols. Linear or branched polyethers are also possible, as they are produced by the polymerization of alkylene oxides such as ethylene oxide, propylene oxide, epichlorohydrin or tetrahydrofuran can be won. Copolymers of this type can also be used. Also suitable are through Addition of the alkylene oxides mentioned to, for example, polyfunctional alcohols, amino alcohols or amines which can be prepared linear or branched addition products.

The starting material for the process according to the invention are preferably polyethers containing at least 2 active hydrogen atoms, preferably with a molecular weight of 750-10,000, in which at least 10% of the hydroxyl groups present are primary OH groups. The primary OH group determination is carried out according to Gorden Hana and Sydney Sigia Journal Vol. 56, pp.297-304 (1962). Such polyethers are made by reacting compounds with reactive hydrogen atoms such as polyalcohols and polyphenols with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin or with mixtures consisting of these alkylene oxides and optionally subsequent modification of the resulting polyethers with ethylene oxide.

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BAD OR | Q | _NAL

2 U υ υ J 9 / I I 8 2

Suitable polyalcohols and polyphenols are e.g. ethylene glycol, Diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 2-butyne- · ,. 1,4-diol, glycerine, 2,4-butanediol, 1,3,6-hexanetriol, trimethylo! Propane, Resorcinol, di-tert-butylpyrocateehin, 3-hydroxy-2-naphthol, 6,7-dihydroxy-1-naphthol, 2,5-dihydroxy-1-naphthol, 2,2- (p-hydroxyphenyl) propane, bis- (p-hydroxyphenyl) methane, Tris (hydroxyphenyl) -elkane, such as 1,1,2-tris (hydroxyphenyl) -methane, 1,1,3-tris (hydroxyphenyl) propane. Other suitable Polyethers are 1,2-alkylene oxide derivatives of mono- or Polyamines of an aliphatic or aromatic nature such as ammonia, methylamine, ethylenediamine, N, N'-dimethylethylenediamine, tetra or Hexamethylenediamine, diethylenetriamine, ethanolamine, diethanolamine, Methyl diethanolamine, triethanolamine, aminoethylpiperazine, Toluydine, o-, m- and p-phenylenediamine, 2,4- and 2,6-diaminotoluene, 2,6-diamino-p-xylene, polynuclear and condensed aromatic polyamines such as 1,4-naphthylenediamine, benzidine, 2,2'-dichloro-4,4'-diphenyldiamine, 4,4'-diaminoazobenzene. as Starting media continue to be embossed with resinous materials of the phenol and resol type.

All of these polyethers are preferred with the use of Ethylene oxide built up, and preferably have at least 10 # primary OH groups. The polyethers mentioned can also by reaction with less than equivalent amounts of Polyisocyanate can be modified.

Other higher molecular weight compounds with active hydrogen atoms are the known polyacetals, polyester amides, Polycarbonates, polyols containing urethane groups. The higher molecular weight compounds to be used according to the invention with reactive Η atoms can also be mixed with low molecular weight compounds with active hydrogen atoms Molecular weights up to 750 can be used. As low molecular weight compounds

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20A0650

with active Waseeratoffatomen come mainly hydroxyl groups containing compounds in embossing, e.g. ethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerine, trimethylolpropane, Castor oil or adducts with molecular weights usually from 200-750 of alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide to such low molecular weight compounds with active hydrogen atoms or to water.

It can also contain higher molecular weight amino groups, as described, for example, in German patent application P 20 19 432.5, can be used advantageously.

This German patent application relates to a method of manufacture of organic compounds of the general formula containing terminal amino groups

-CO-X-

in which

η is an integer from 2 to 8, X is oxygen or sulfur and

R represents an n-valued remainder as it can be obtained by removal the hydroxyl or mercapto groups of an n-valent polyalkylene ether polyol or of a polyalkylene thioether polythiol is obtained

characterized in that compounds of the general formula

of molecular weight 600 to 10,000 with at least η equivalents to isatoic anhydride in the presence of strong bases to react.

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In this case arise in contrast to those previously described Polyurethane plastics as chain links do not have urethane groups, but rather alongside 'ester and ether groups Plastic containing urea groups «.

Conventional polyisocyanates can be used as isocyanates Embossing, advantageously are used:

1,4-butane diisocyanate, 1,6-hexane diisocyanate, 1,8-octamethylene diisocyanate, furthermore carboxylic acid ester diisocyanates, cycloaliphatic diisocyanates such as i-methyl-cyclohexane-2,4- and 2,6-diisocyanate and any devices of these isomers, cyclohexane-1 , 4- and -t, 3-diisocyanate, 4>4'-dicyclohexylinethane diisocyanate, isophorone diisocyanate, araliphatic diisocyanates such as 1,3- and 1,4-xylylene diisocyanate, aromatic diisocyanates such as tolylene diisocyanate- (2,4) - and - ( 2,6) as well as any mixtures of these isomers, 1,3- and 1,4-phenylene diisocyanate, 414'-diphenylmethane diisocyanate, 1,5-naphthylene _{diisocyanate #} triisocyanates such as 1,3,5-benzene triisocyanate or 4,4 ', 4 '' -Triphenylmethane triisocyanate can be used proportionally. According to the invention, 2,4- and 2,6-toluene diisocyanate and its isomer mixtures, 4,4'-diphenylmethane diisocyanate and 1,5-naphthylene diisocyanate and polyphenylpolymethylene polyisocyanates, as can be prepared by aniline-formaldehyde condensation and subsequent phosgenation, and their mixtures with toluene are preferred -2,4- and / or-2,6-diisocyanate, optionally mixed with 4,4'-diphenylmethane diisocyanate and its isomers.

According to the invention, solutions are also preferred as polyisocyanates of so-called "modified polyisocyanates" J i.e. as Polyisocyanates Solutions of polyisocyanates containing biuret groups in polyisocyanates free of biuret groups and / or solutions of at least two NGO groups and at least one. ] f, N'-i-substituted Allophanaic acid ester group

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tion containing polyisocyanates in allophanaic acid ester groups free polyisocyanates and / or solutions of reaction products from hyisocyanates and bivalent / or polyvalent hydroxyl groups containing compounds in urethane-free polyisocyanates and / or solutions of more than one NCO group and at least a polyisocyanate containing isocyanuric acid ring in isocyanurate-free polyisocyanates.

The invention according to preferred solutions of the ⁿ modified polyisocyanates "have 9t weight usually a content of 1 to 85, preferably 10 to 50 wt .- ^., In" modified polyisocyanates

The allophanate polyisocyanates can be prepared, for example, in accordance with German patent application No. P 20 08 064.8. Diisocyanates such as toluene-2,4-diisocyanate or mixtures thereof with toluene-2,6-diisocyanate are preferably used for this purpose. ·.

As modified polyisocyanates to be used according to the invention There are also solutions of polyisocyanates containing biuret groups in polyisocyanates free of biuret groups. According to the invention, 1 to 85% strength by weight solutions of biuret group-containing polyisocyanates of the general type are preferred Formula:

0
OCN-RNGNR- NCO

OCH -RNC = OX
1
X

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lkylrest to C ₁₀ -cycloalkyl ^a, O, in which R is a C ₁ - - "to CjQ alkyl, C _5" - to C ₁₂ * - ^{ä; ca} l ^k y ^{lres "fc} or Cg to CjQ-aryl and X is hydrogen or the moiety

R - NGO

denotes in which R has the meaning already mentioned and η is an integer from 0-5, in biuret-free polyisocyanates, the proportion of biuret polyisocyanates with more than three isocyanate groups, based on the total amount of biuret polyisocyanates, being at least 20% by weight. Polyisocyanates containing biuret groups can be prepared, for example, according to the teaching of British patent specification 889 050 or according to German patent specification 1 101 394-. Polyisocyanates preferred according to the invention are solutions of polyisocyanates containing biuret groups, which are obtained either by reaction of 2,4- and / or 2 _i 6-toluene diisocyanate, 4 _f 4'-diphenylmethane diisoeyanate and / or its isomers or a polyisoeyanate mixture fet obtained by aniline-formaldehyde condensation and subsequent phosgenation, prepared with water or formic acid, in biuret-free polyisocyanates. The polyisocyanates to be used according to the invention preferably contain 0.03-5% by weight, preferably 0.1-2% by weight, of chemically bound emulsifiers. These emulsifiers are -OH, amino, amido, CO ^, -SH, or urethane groups and are therefore possess ction by _a Re with the isocyanate groups in the polyisocyanate is installed in accordance with the teachings of the German patent application P 19 63 189.1.

As a starting material according to the invention furthermore as Isocyanate components used are those polyisocyanates which are characterized by a content of polyisocyanates containing urethane groups and possibly a higher branching

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degree as pure difunctional isocyanates. These · : · Isocyanates often have a content; of isocyanates containing urethane groups from 10-70 $, preferably from 20 - 5056, dissolved in polyisocyanates free of urethane groups.

The modified polyisocyanates are also solutions of at least a polyisocyanate containing isocyanuric acid ring is used in liquid polyisocyanates free of isocyanurate groups. Such Polyisocyanates containing isocyanurate groups and processes for their preparation are described, for example, in German patents 951 168, 113 869, 112 285, 1 022 789, 123 729 and in British patents 89 809, 821 158, 827 120, 856 372, 927 173, 920 080, 952 931, in American patents 3 154-522, 2 801 244, in French patent specification 1 510 342 as well as in the Belgian patent specification 718 994 called. Preferred polyisocyanates which have at least one isocyanuric acid ring are polymeric toluene-2,4- and / or-2,6-diisocyanates, optionally mixed with 4,4'-diphenylmethane diisocyanate or its isomers. These isocyanates to be used according to the invention are obtained in such a way that by the polyisocyanate containing ieocyanurate groups usually in amounts of 1-85% by weight, based on the Weight of the resulting polyisocyanate solutions, dissolves in the liquid polyisocyanates free of isocyanurate groups.

As urethane groups or. Allophanate groups or isocyanurate groups or biuret-group-free polyisocyanates can be aliphatic, cycloaliphatic, aromatic or araliphatic isocyanates are used, e.g. in Liebige Annalen der Chemie, Volume 562 (1949), page 755 and the following. Tolylene diisocyanate or its Isomer mixtures or such non-distilled isomer mixtures, Diphenylmethane-4,4 ', - 2,4'-diisocyanate or not distilled raw material, naphthalene-1,5-diisocyanate, triphenyl-

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methane 4,4 ¹ , 4 ^tl -triisQcyanat, isophorone diisocyanate, polyphenylpolymethylene polyisocyanates obtained by condensation of aniline and / or a-alkyl-substituted anilines with formaldehyde and subsequent phosgenation, carfcodiimide isocyanate adducts, such as isocyanate adducts. are obtained according to the German patent 1 092 007 * ι

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The production of the self-extinguishing polyurethane foams takes place in Hegel using the known one-shot method. After the one-process shot takes place, the foam production at room temperature and / or elevated temperature by simple '. · Mixing of the polyisocyanates according to the invention described with the höheriDolekularen polyols, v / ater and / or other blowing agents, if appropriate emulsifiers and other excipients and the auxiliaries according to Invention can be used. In this case, machine devices are advantageously used, such as, for example, in French patent specification 10 747 143, or the methods as described in German patent specification 881 881.

Suitable emulsifiers are e.g. ethylene oxide or ethylene oxide / propylene oxide adducts, to substances containing hydrophobic hydroxylalkylene or amino groups or amido groups. As catalysts for the production of flame-retardant, non-shrinking foams containing urethane groups v / earth tertiary amines and / or silaamines, H-substituted aziridines, hexahydrotriazines, optionally used in coordination with organic metal compounds, the one different contribution to the acceleration of the one deliver partial reactions occurring during foam formation. While amines prefer to catalyze the blowing reaction, we ^ kcn organic metal compounds preferentially on the crosslinking reaction a. Depending on the constitution of the amines or silaamines used, the catalytic efficiency on the pull reaction, i.e. for example the reaction between isocyanate groups and water with the release of carbon dioxide be different in strength. To achieve technical sales favorable reaction times depending on the particular constitution of the chosen catalyst or of the catalyst mixture, the amount to be used empirically determined. Compounds which are well known for the production of polyurethane chemicals can be used as amines such as Diinetbylbenzylaniin, N-Hethylmorpho-

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Iin, lriäthyle2idiamin _} Mmethylpiperazin, 1,2-DiinethyliiBiclagol, Bimethylüthanolanjin, Diethanolamin, Triäthanolarain, Diethylaminoäthanol, II, H ¹ J! ", !!" piperazine »^.

Silicon compounds containing carbon are used as silaamines Contain silicon bonds, as described, for example, in Putschen patent specification 1 229 290 "and. As examples eeien mentions 2,2,4--2? rimethyl - 2-egg aorpholine, 1,3-egg ÄtbylaiflinoBiethyltetranjetbyldisiloxan. But it is also based on nitrogenous bases such as TetraalliylammoniuiGhydroxi.de as well as-. Alkalis, alkali phenolates or alcoholates such as, for example Katriurjiaethylat pointed out. If necessary in combination wit amines, silaroins and hexahydrotriazines according to the '-belgi * - Bcheu Godfather Code 730 $ 56 * »ingesetsit organic Metal compounds are preferably organic tin compounds, o.B. 2 »inn ~ (II) -oetoate or bibutyltiliumilaurate.

Additives for regulating cell structure can be we also use organic or inorganic pull materials in & Parbs or plasticizers such as phthalic acid esters.

The raw materials produced by the process according to the invention are flame retardant with known type of flame retardant additives and in the sense of the test ASTM - D 1692 - 67 T as self-extinguishing to call. This highly desirable property can be achieved through the inclusion of known Flame retardants, such as 2 ".B. Trichloro and tribromo alkyl phosphates Achieve, this property under extreme storage conditions , such as high temperatures over long periods of time, is partially lost. Enduring and at the same time essential Improvement of the already good flame resistance of the

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Driving products can be modified, for example the modified polyisocyanate solutions with built-in ^ i.e. reactive to isocyanates ** containing hydrogen Achieve chlorine and / or bromine-containing compounds. With regard to the effect achieved, it is irrelevant which one Place these built-in flame retardants, for example, whether they are introduced directly into the modified polyisocyanate built in or whether they are subsequently added to the polyisocyanate solutions or reaction mixtures.

Examples of flame retardants that can be built in are: ^ 2-chloroethanol, 2-bromoethanol, trichloroethanol, 1,3- and 1,2- ' Dichloropropanol, 2-bromopropanediol, 1,1-

Styrene chlorohydrin and styrene bromohydrin, bromoacetic acid.

The elastic ones accessible depending on the method according to the invention and semi-elastic foams are used, for example, as cushioning materials, mattresses, packaging materials, Foils for lamination purposes, insulating material and because of their flame resistance in those areas where this property is particularly valued, e.g. in automobiles, in aircraft construction and general transportation. The foams can either be produced by the foam-molding process or by making up from block foamed material.

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Example 1; «*

Chain extender

4,4'-diamino-diphenylmethane-3 »3'-dicarboxylic acid dimethyl ester

(Melting point: 146 ⁰ C)

200 g of ethylene glycol obtained from adipic acid and polyester (OH number 56) are dehydrated in vacuum at 130 ° C and at 12O ⁰ C with 40 g of an isomeric mixture of 80 weight percent 2,4- and 20 weight percent 2,6-tolylene diisocyanate was added.

The reaction mixture is stirred for a further 30 minutes, evacuated for 30 seconds to remove air, and 36.6 g are left with stirring of the melted chain extender.

30.9 g of 4,4'-diamino-diphenylmethane-3,3'-dicarboxylic acid dimethyl ester are used as a chain extender. After heating for 24 hours at 100 ^° C., a highly elastic polyurethane plastic is obtained with the following properties:

kp / cm

tensile strenght (DIN 53504) 350 Elongation at break (DIN 53504) 527 Shore hardness A (DIN 53505) 91 elasticity (DIN 53512) 27 Example 2:

Chain extender

4,4'-diamino-diphenylmethane-3,3 ^f -dicarboxylic acid diethyl ester (melting point: 109 ° C)

The procedure is as described in Example 1, but 32.9 g of 4,4 ^f -diamino-diphenylmethane-3f3'-dicarboxylic acid diethyl ester are used. After 24 hours of annealing time at 100 ⁰ C, an elastomer having the following properties gives:

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Tensile strength (DIN 53504) 375 kp / cm ²

Elongation at break (DIN 53504) 545 #

Shore hardness A (DIN 53505) 89

Elasticity (DIN 53512) 31 t

Example 3 t

Chain extender

4,4'-diamino-diphenylmethane-3.3 ^l -dicar "bonsäuredimethyleeter

Component A

A mix of

50 parts by weight of 4,4'-diamino-diphenylmethane-3 * 3'dicarbon-

acid dimethyl ester and

50 parts by weight of a triamine, which by conversion of

Isatoic anhydride is obtained with a polyether (hydroxyl number 56). The polyether produced by propoxylation of glycerine and subsequent ethoxylation (weight ratio of propylene oxide to ethylene oxide = 55:

Component B

730 parts by weight of a polyether made from dipropylene glycol and propylene oxide, OH number 148) become

660 parts by weight of 2,4- / 2,6-tolylene diisocyanate (80:20 wt. ^) Under

Stir added dropwise. The temperature rises to 50 ⁰ C. The mixture is then ^{heated up to 80 °} C. and kept at this temperature until the NCO content is 17 l .

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100 parts by weight of component A are heated to 140 ° C. and mixed with 107 parts by weight of component B, which was also heated to 140 ° C., by means of a stirrer (3000 KpM) for 10 seconds. The mixture is poured into an open metal mold, and then cured at 110 ⁰ C in an oven (approximately 1 hour).

Physical values of the molded part:
Elongation at break from tensile test: 150%

Dimensional stability in the heat under bending stress, according to DIN 53 424, bending stress approx. 3 kp / cm at 10 mm, deflection ^ -jo * ¹¹⁰ ° ^C *

Example 4s

100.0 parts by weight of a polyether prepared by reaction of propylene oxide and then ethylene oxide with trimethylolpropane, so that terminal about 60 $ primary hydroxyl groups and one OH number of 36.0 results,

2.5 parts by weight of water

0.3 part by weight of endoethylene piperazine, 0.5 part by weight of tetramethylethylene diamine 2.5 parts by weight 4,4'-diaminodiphenylmethane

3.3 ^l -dicarboxylic acid dimethyl ester

are mixed together and 39.8 parts by weight of one Polyisocyanates containing allophanate groups (HCO content 35 »1/6) made from trimethylolpropane, 2,4- and 2,6- {dolylene diisocyanate (Isomer ratio 80i: 20 wt. #) And 2,3-dibromopropanol-1, brought to reaction.

Le A 13 169 - 23 -

209839/1182

Production of the polyisocyanate:

134 parts by weight of trimethylolpropane and tolylene-2,4-2,6-diisocyanate in the course of about an hour submitted, heated to 80 ⁰ C (isomer ratio 80: 20) added to give the reaction mixture to 114 ° C warmed up. After reaching einee content of 41 »3% NCO immediately after the end of the trimethylol propane was heated to 150 ⁰ C and left for 20 hours at this temperature. The result is a solution of an allophanate polyisocyanate in a mixture of toluene diisocyanate isomers with an NCO content of 38.1 $ and a viscosity of 77 cP ^

1 to 900 parts by weight of this solution, 100 parts by weight of 2,3-dibromopropanol-1 was added and reacted for 2 1/2 hours at 90 ⁰ C at 80 ° C. The modified allophanate polyisocyanate in tolylene diisocyanate isomer mixture is characterized by a content of 35.1% NCO, a Vieko-

25 ° _ /

sity of 11Θ cP and solids content of 41%.

A foam with the following mechanical properties is obtained:

Volume weight according to DIN 53420 (kg / m ⁵ ) 43

W Tensile strength according to DIN 53571 (kp / cm ² ) 0.7

Elongation at break according to DIN 53571 (%) 150

Print attempt at 40% collapse

pressure according to DIN 53577 (p / cm ² ) 25

Compression set 50%

according to DIN 53572 _{5 | 0}

Le A 13 169 - 24 -

20Ü839 / 1 182

Example 5

100.0 parts by weight of a polyether * produced by reaction of propylene oxide and then ethylene oxide with propylene glycol-1,3, so that at the end approx. 60% primary hydroxyl groups and an OH number of 28.0 resulted,

2.5 parts by weight of water

0.3 parts by weight of Endoäthylenpiperazin 1.0 parts by weight of triethylamine

1.0 part by weight 4,4'-diaminodiphenylmethane

3,3 '-dicarboxylic acid dimethyl ester

are mixed together and 39 »4 parts by weight of one Isoeyanatadduktes (NCO content 35%) from trimethylolpropane and 2,4- and 2,6-tolylene diisocyanate (isomer ratio 80:20% by weight) produced, reacted. A foam with the following mechanical properties is obtained:

Volume weight according to DIN 53420 (kg / nr) 42

Tensile strength according to DIK 53571 (kp / cra ² ) 0.8 elongation at break according to DIN 53571 (%) 180

Compression test at 40% compression according to DIN 53577 (p / cm ² ) 23

Compression set 50%

according to DIN 53572 4.5

Le A 13 169 - 25 -

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Example 6;

100.0 parts by weight of a polyether prepared by reacting propylene oxide and then ethylene oxide with
Trimethylolpropane, so that at the end approx. 60? Ί primary hydroxyl groups and an OH number of 35.0 result,

2.5 parts by weight of water

0.1 part by weight of endoethylene piperazine

0.1 part by weight of tin (II) dioctoate

0.5 parts by weight of N ^A methylmorpholine

1.0 part by weight 4,4'-diaminodiphenylmethane

3 »3'-dicarboxylic acid dimethyl ester

are mixed with one another and with 40.2 parts by weight of a polyisocyanate containing biuret groups, which has been prepared by reacting a mixture of 2,4- and 2,6-toluene di3ocyanate (isomer ratio 80:20% by weight) with water (NCO content 38, 5 #), i * ^{1 of} a closed mold is made to react.

A foam with the following mechanical properties is obtained:

Volume weight according to DIN 53420 (kg / m ⁵ ) 40

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

Elongation at break according to DIN 53571 (#) 160

Compression test at 40 # compression according to Din 53577 (p / cm ² ) 27

Compression set

according to DIN 53572 3.6

Le a 13 169 - 26 -

209839/1182

Example 7 s

100.0 parts by weight of a polyether prepared by reaction of propylene oxide and then ethylene oxide with glycerol, so that terminal about 60 $ primary hydroxyl groups and an OH number of 35.0 resulted,

2.5 parts by weight of water

0.2 parts by weight of Endoäthylenpiperazin 0.5 parts by weight of tetramethylethylenediamine 5 i 0 parts by weight of 4,4'-diaminodiphenylmethane

3,3'-dicarboxylic acid dimethyl ester

are mixed with one another and with 35.7 parts by weight of a mixture (NCO content $ 38.5) and 40 parts by weight of a polyphenylpolymethylene / polyisocyanate as obtained by aniline-formaldehyde condensation and subsequent phosgenation (NCO content $ 31) and 40 parts by weight of a 2,4- and 2,6-toluylene diisocyanate mixture (65% by weight of 2,4-tolylene diisocyanate), brought to reaction.

A foam with the following siselianie properties is obtained:

Volume weight according to DIN 53420 (kg / m ') 46

Tensile strength according to DIS 53571 (kp / cm ² ) 0.6

Elongation at break according to DIN 53571 (#) 140

Compression test at 40 $ compression according to DIN 53577 (p / cm ² ) 15

Compression set $ 50

according to DIN 53572 2.6

Le A 13 169 - 27 -

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Example 8;

100.0 parts by weight of a Polyäthera _t produced by the reaction of propylene oxide and then ethylene oxide with trimethylolpropane, so that at the end about 60 $ primary hydroxyl groups and an OH number of 35.0 resulted,

2.5 parts by weight of water

0.2 part by weight of endoethylene piperazine 1.0 part by weight of triethylamine

5.0 parts by weight 4,4'-diaminodiphenylmethane

3,3'-dicarboxylic acid dimethyl ester

are mixed together and with 35.7 parts by weight of a mixture (NCO content $ 39.5) of 60.0 parts by weight of 2,4-tolylene diisocyanate, 10.0 parts by weight of 2,6-tolylene diisocyanate and 30.0 parts by weight of a polymerized 2.4 -Toluylene diisocyanate (NCO content $ 20.8), brought to reaction.

A foam with the following mechanical properties is obtained:

Volume weight according to DIN 53420 (Kg / m- ⁵ ) 40

Tensile strength according to DIN 53571 (kp / cm ² ) 0.8 elongation at break according to DIN 53571 (%) 170

Compression test at 40 $ compression according to DIN 53577 '(p / cm ² ) 17

Compression set 50? O

according to DIN 53572 6.6

Le A 13 11 »9 - 2β -

2 UJ ti j J ι i ι Β 2

Claims (1)

Patent claims: aromatic diamines of the general formula containing ster groups ROOC. COO-R ' in the R and R ^{1 are the} same or different and C ^ -C ^ g-, preferably Cj-Cg-alkyl radicals, C - C ^ ^, - cycloalkyl radicals or Cg-C ₁ »-aryl radicals, R "and R" ^{r are} identical or different and are hydrogen R "or Cj-Cg-alkyl radicals or —C— R ¹¹¹ represent leftovers. 2. Process for the preparation of ester groups aromatic diamines of the general formula ROOC in the R and R ^{1 are} identical or different and C ^ -C ₁ Q-, preferably Cj-Cg-alkyl radicals, C ^ -C ^ cycloalkyl radicals or Cg-C .. aryl radicals, R "and R" ^{1 are} identical or different and are hydrogen or C.-C ^ -alkyl radicals or R " R "* Represent C ^ -Cg-Cycloalky lenreste. characterized in that compounds of the formula ha A 13 169 - 29 - 2 0 U 8 i 9/1182 in the R and R ^{1 are} identical or different and C _x -C ₁₀ -. before- preferably C ^ -Cg-alkyl radicals, C ₄ -C _1. -cycloalkyl en- mean radicals or C ^ -C * j-aryl radicals, with aldehydes or ketones of the formula ^RIts * c = o R "' in the R "and R" · are identical or different and are hydrogen or C ₄ -C alkyl radicals or ft » ^{1 b} Represent C -C ₆ -CyCloalkylene radicals. condensed and the condensation product rearranged by the action of acids at 40-130 ^{0 C.} A process for Hers La FILLING of optionally cellular ^(T rethangruppen having plastics from polyisocyanates, high molecular weight active Waaaerstoffatome containing compounds, aromaLi sehenDiamLnen, optionally water and / or Andren Treibmi tteLti, catalysts, emulsifiers and adjuvants, characterized in that the aromatic compounds of the general formula ; ROOC in the Le A15 169 209839/1182 BAD original R and R 'are identical or different and C ^ -C -jg- »preferably Cj-Cg-alkyl radicals, C ^ -C ₁ ^ cycloalkyl radicals or C ₆ -C ₁ ^ -aryl radicals, · R "and R" 'are identical or different and are hydrogen or C, -C _i - ~ alkyl radicals or
R " ^{1 6} Represent C.-Cg-Cycloalkylene radicals. be used. Φ. The method according to claim 3, characterized in that as higher molecular weight compound with active hydrogen atoms polyether having at least two active hydrogen atoms and a molecular weight of 750 to 10,000, preferably 4,000 to 10,000, in which at least 1036 of the existing OH groups are primary hydroxyl groups. 5. The method according to claim 3 and 4, characterized by that the polyisocyanates are solutions from at least two NGO groups and at least one NjN'-disuhstituIer ^ a Ällophansäureestergruppierung containing polyisocyanates are used in liquid polyisocyanates free from allophanic acid ester groups will. 6. The method according to claim 3 and 4, characterized in that the polyisocyanates 1-85 wt .- $ solutions of biuret groups containing polyisocyanates of the general formula: 0. OtH -RHCNR- UCO II. C-OX
I. XN
I.
R - NCO Le; · 13 169 - 31 - -, ι ·.,. y ι / ■ · ο-- »BAD ORIGINAL to CjQ cycloalkyl radical, CRJ to C ₁₂ "aralkyl, or C ^ - - in which R is a C ₁ - to CjQ alkyl, C ₅ to CjQ aryl group and X is hydrogen or the group X = - (- CON -) ~ _n HR - NCO means in which R has the meaning already mentioned and η represents an integer from 0 to 5, in biuret groups-free Polyisocyanates, the proportion of Biuretpolyjsocyanaten with at least 3 isocyanate groups, based on the total amount of polyisocyanates is at least 20% by weight, be used. 7. The method according to claim 3 and 4, characterized in that the polyisocyanates are solutions of 10 to 70 wt .- $, preferably 20 to 50 wt .- $ of NCO groups containing reaction products of polyisocyanates and divalent and / or compounds containing higher hydroxyl groups can be used in polyisocyanates free of urethane groups. 8. The method according to claim 3 and 4, characterized in that that, as polyisocyanates, solutions of 1 to 85% by weight, preferably 10 to 35% by weight, of at least one isocyanuric acid ring containing polyisocyanates are used in polyisocyanates free from Iaocyanuratgruppen. 9. The method according to claim 3 and 4, characterized in that the polyisocyanates are toluene-2,4- and / or -2,6-diisocyanate and / or polyphenyl-polymethylene-polyisocyanates, optionally mixed with 4,4'-phenyl-methanediocyanate and / or its isomers can be used. Le A 13 169 - 32 - 209839/1182 10. The method according to claim 3 "to 9, characterized in that that additional flame retardants are used. Le A 13.169-33- 209839/1 182