DE2030233A1 - N,N'-Substd.-2,4,5-triketo-imidazolidine - and oxamido-acid alkyl esters tri keto imidazolidine - Google Patents

Abstract

N:N'-Substd. 2:4:5-triketo-imidazolidines, which in the form of their low mol. wt. products find application as intermediates for various organic syntheses, as starting materials for medicaments and parasiticides, as stabilisers for condensation and polymerisation resins, as temp.-resistant formed products, as coatings for metals, and ceramics, and as mouldings contng. glass fibres or graphite fillers, are produced by reacting oxamido-acid alkyl esters contng. the gp. -NH-CO-COORv (where Rv is aliphatic hydrocarbon gp. with is not >18C, cycloaliphatic is not >8C hydrocarbon gp., mononuclear aromatic hydrocarbon gp. opt. replaced by hydrocarbon gps. with is not >14C) at -20 degrees C. to +280 degrees C. in the presence or absence of a catalyst with isocyanates or cpds. dissociating into isocyanates and with polycarbonic acids which are aromatic, satd. or unsatd., olefinic, dibasic-hexabasic with 4-70C atoms and/or their anhydrides to form condensates contng. amide and/or imide gps.

Description

aeo »" Scr * "<& ** - * L fe *« - itte- '

REICHHOLD-ALBERT-CHEMIE AG., HAMBURG 70, IVERSSTRASSE 57

Patent application

Process for the production of modified NN ¹ -substituted ._ _ 2,4,5-Trlketoimldazolldlnen _____

The invention relates to a process for the preparation of modified N-N'-substituted * 2,4,5-triketoimidazolidines by reacting alkyl oxaridates with isocyanates or isocyanate-releasing compounds, the oxamic acid esters having an -NH-CO-CO-OR ^{7 group} have, wherein R ^{v is} an aliphatic hydrocarbon radical with up to 18, preferably up to 6 carbon atoms, a cycloaliphatic hydrocarbon radical with up to 8 carbon atoms, a mononuclear aromatic hydrocarbon radical which may be substituted with hydrocarbon radicals with up to 14 carbon atoms can means - in general at temperatures from -20 to + 28o * C and optionally in the presence of a catalyst.

It has already been proposed to react alkyl oxarate with isocyanates to form N, N ^f -substituted 2,4,5-triketoimidazolidines. The conversion can take place according to equation (1) of the attached formula sheet. The second mole of isocyanate serves as a condensation agent in the formation of the imidazolidine ring.

As has also been suggested, this reaction is particular interesting for the production of precondeneates, the still contain linkable end groups, e.g. according to equation (2) of the attached formula sheet.

- 2 109 852/1923

The end groups -NH-CO ^ COQR ^v and -NH-COOR ^V contained in the precondensates can be converted into poly-2,4,5 »triketoimidazolidines upon thermal treatment with elimination of alcohol according to equation (3). It has been suggested earlier that this sequence of reactions is capable of great generalization.

In equations (2) and (3),

R a single or multi-core ©! ¹ mono- to low-valent aromatic or heteroaromatic residue with up to 20 carbon atoms, which may contain halogen * Mitro-p di »'alkylamino, diarylamino, alkylsry, amino groups, AlEq ?! ^ _x , alkoxy, carboxyalkyl, carboxyaryl, aoyl, for example acetyl, cycloalky! groups or halogenated alkyl, alkoxy, carboxyalkyl, carboxyaryl «acyl, s _a B <. Actyl, cycloalkyl groups "Sintiich is substituted with up to 18 C-atoms, whereby the aromatic radicals can also be quinones if R is bound to an oxamic acid" or if this "Eeterrest is zero and where polyvalent © • aromatic Residues can be linked to one another by aliphatisoh® residues or by heteroatoms,

R ^m has the meaning given under R or denotes an aliphatic hydrocarbon radical with up to 18 carbon atoms or a cycloaliphatic hydrocarbon radical with up to 12 carbon atoms.

The precondenses obtained after the reaction of Equation (3), which contain triketoimldazolidia rings, generally have a relatively low molar value. Di © s @ V © r "bonds have" proven itself well but it was erwttosciit for some purposes to use _# Connect "ag © a higher molecular weight, it to the App @ ndungsmögli © hk © still expanding and their Handhabiing to improve.

109852/1923

According to the invention, this is achieved by additionally adding Polycarboxylic acids, which are at least dibasic and e.g. hexavalent, preferably at most tetravalent carboxylic acids and / or their anhydrides, if such exist, implemented so that condensation products form, the AmId- and / or included groups *

The method according to the invention thus enables production from monomeric condensation products to high molecular weight, the at the same time 2,4,5 * Trlketoimidazolidine and polyamides, -imides or polyaiaidoimides. Compounds that are a combination These different groups have »are characterized by particularly good processing properties.

It is not necessary to use the mixtures of the reactants; rather, it is also possible to carry out the reaction in such a way that one partner is initially introduced, possibly in a mixture with only an insignificant proportion of the second and optionally the third partner and then the main amount of the second and optionally third reaction partner is added. This embodiment can be carried out both in solution and in the melt. A catalyst can be added to the initially introduced reactant and / or to the one used later. It is also possible initially to react only two components with one another and the third in a further stage. For example, the polycarboxylic acids can first be reacted - at least partially - with the isocyanates, for example with irald or amide formation, whereupon in the second stage the reaction with the oxaraldic acid ester and optionally in a further stage (a reaction with the remaining polycarboxylic acid) takes place. This reaction in two stages is illustrated, for example, in equations (4) and (5). Since the product still contains reactive groups on both sides, these can generally be extended with other isocyanate groups and, if appropriate, older oxaraidic acid groups with chain extension, eg »outer amide or Iraidblldungg according to equation '(6) and possibly uv her. Failure to respond, Xn des

Equations 4 to 6 mean

Usually one optionally by alkyl, halogen or amino groups substituted trivalent aliphatic acids, oarbo * or heterocyclic, mono- or polyvalent, ι e.g. cycloaliphatic, aliphatic-aromatic or aromatic hydrocarbon residue from 2 to 20 carbon atoms

"IV and R ^v can be the same © or different and aliphatic" hydrocarbon radicals with up to 18 carbon atoms, cycloaliphatic hydrocarbon radicals with up to 8 carbon atoms, mononuclear aromatic hydrocarbon radicals with 6 carbon atoms, which are not substituted. or with hydrocarbons

Substance residues are substituted with up to 14 carbon atoms, mean.
In compound VI, the ketfoenv © Fteüpfimg. After the reaction of the anhydride groups. The compound "f mit d © ra leocyanat Il äarge" is obtained then geiaiß Gleteta & g '(55 wi @ d © r alt 0xai3idsäiÄ> e © g "ter react widely with formation of triicetoisniuazolidinpingaa. The free®" ester group of the Verbinöimg- ¥ can with ZmB, with compound II _ß III

Formation of further Triltefeoiraid & zoliote ^ iage react ₀ -Di © geniES Oldiehung (4) to (6) © success @ n wat © r escape of alcohol or "carbon oxych Si" represent condensations "and are directly related to tricarboxylic acids" to analogous "W © is ©, di- and other polycarboxylic acids can also be converted »

In the products obtained according to the invention, the same residues as in the compounds I or IV can form the structural groups, but Eb is also possible, ύ & Β ossanidic acid »ester groups on both sides or these ester groups only on one side and on the other side in each case. or xsoeyaa grids or urethane or isoeyane residues are arranged on both sides «

109852/192

BATH ORIGINAL

Depending on the reaction conditions, the process according to the invention can lead to monomeric or polymeric compounds. In the reaction according to the invention, branched monomers or polymers can also be obtained if, for example, triisocyanates, at least trivalent carboxylic acids or at least trivalent oxamic acid esters or a mixture of these polyvalent components - optionally in a mixture with mono- or divalent components - starts. If the branching is to take place on the trioarboxylic acid residue, the free acid, for example, should be analogous Equation (4) can be reacted with three moles of isocyanate, so that an amide linkage takes place in three directions.

Monomeric compounds can be produced e.g. with three or more triketoimidazolidine groups. This is the case, for example, if one starts from monooxamic acid esters and Triieocyanaten. at However, when preparing these compounds, care should be taken that the amino groups in the cyclic radical R are not in the o-position are arranged. Further products of this reaction are compounds according to the formulas XXIX and XXX (see formula sheets). In this, R has the meaning given above.

R "has the meaning given under R, where R and R ^{MI can be} identical or different,

R " ¹ has the ^{meaning given under R f} , where R ¹ and R ^{WI can be} identical or different and R ^{ni is} at most tetravalent,

denotes a bivalent or trivalent, optionally substituted by alkyl, halogen or amino groups aliphatic, carbon * or heterocyclic, single or polynuclear, e.g. eyeloaliphatic / aliphatic-aromatic or aromatic hydrocarbon radical with two to 20 carbon atoms, also mean

x zero if y «1, or 1,

y zero or an integer from 1 to 70,

ζ an integer from 1 to 6, preferably 1 to 3, and at least two when Q «is zero; ·

i and k can in each case be the same or different and -NH-CO- or

BATH AL

g and h each 1 or 2, with the Sum® of (g + h) at most

3 is
d, β, f and J Jewe ≤ the number one or zero »where the sum of (d + e + f + J) is at least 1 and

where one of the radicals R and R is always " ^f aresaat! sch and _fl if R ^{! n is} aliphatic or cyeloaliphatiseli, de? R" ^! adjacent radicals R, R ¹ or H ″ are always aromatic

As can be seen from Formula XXIX and the 2sug @ Mpig @ n definition, Hp _{oly is} here only as two «
represents. But it is without
three-valued, e.g. four- to
In this case, R _{poly is} a four to four-eighth radical, g and h each mean an integer from 1 to 5 _S where (g + h) is at most 6. Then at R _DoiY © in © branch can occur, for example from form ©! XXXI can be seen.

On the other hand, it is also possible that the branching point is contained in a radical R *. In the compounds according to formula XXIX, R, R ¹ , R "and R" can also be branched due to their polyfractionality. A product obtained according to the invention * in which: the branching is in the remainder of R ¹ , shows Fora »! XXX. Bafin I, the square brackets have the same meaning «as in Formula XXIX. " _:

The molar ratios of the partners QxamidsSureeeter, Iso-.

cyanate and polycarboxylic acid can be varied within wide limits be ».You can get to grips with the following equation reproduce!

(* .A ⁽ + cG ¹ ) - (bB ¹ )

In it mean

a is the number of Oxamidäiire®at®rgroupptn in A "moles acid esters,

- b the number of Iaocyanafcgrupp © E in B 'Molei ο the number of carboxyl groups in O ⁹ moles

109852/1923 SAO i

here & and b mean whole numbers from 2 to 4 and ο an integer from 2 ble 6. A * means 0.97 ble 0.0} mol «C * means 0» Qj5 to 0.97 mol «where the Sunne of A ¹ and C ^! always 1 let «, (bB ¹ } can be up to three times, preferably up to 1.1 times larger than (aA ¹ + e.C ') ·

The oxamic acid esters, isocyanate and polycarboxylic acids can each be present as the sole representative of their substance class or as Gern Ische.

In the reaction between the oxaidic acid esters, the isocyanates and the polycarboxylic acids can be products with only the reaction conditions given above moderately high degree of polymerisation obtained in this reaction For example, one mole of BlsoxaidsKureester with one mole Diisocyanates and then react with one mole of a single di- or tricarboxylic acid anhydride or the free acid, although only one isocyanate group is used for ring formation, while the other assumes the role of condensation, i.e. that the alcohol released during ring closure intramolecularly in the The connection formed is anchored in the form of a lip-thang group. This urethane group, which can also be referred to as a blocked leocyanate, is now set, for example, in the case of increased Temperature with or without a catalyst with elimination of alcohol and carbon dioxide with the carboxyl group of an amide or imide group. This reaction proceeds according to equation (8) below Formation of compound XXXIII. But there can also be multiple Forms of the compound XXXIII arise «In this case is in this connection / greater than 1. In these cases, the at Alcohol released from the ring closures intramolecularly in the polymer and / or extramolecularly to unreacted * isocyanate be bound. These products can be the end groups

H 1

R ^V OCC-NH-, -NH-C-OR ^, - COOH, ~ CQQR ^V , -COOR ^ and -NC = O

IV Y-

contain. R mi-J. R can then be versähiedea if a mixture of Oxamiiie'ijireeßfcern old under; Medllohen alkyl groups is used .. ".105852 / _: U2 ';

bad ^

As is easy to see, the new process enables the implementation of very different starting materials.

The claimed method offers further advantages. While, for example, the conversion of polycarboxylic acids, which is known per se or their anhydrides with polyisocyanates at temperatures above 80 ° C. often result in insoluble imide groups Polymers which are extremely difficult to process lead to the implementation of the same reaction partners with the use of an oxamidic acid ester in the above specified proportions of clear polymer solutions.

The process according to the invention can be expanded within a wide range. Perform temperature range ,, Thus, the reaction Tonn in the absence or advantageous - in the presence of solvents at temperatures of -20 to ¹³ C -8-280 _1, preferably at ⁰ ° C to l80 ^e C _e effected. The reaction is exothermic and in many pills already takes place at room temperature or slightly elevated temperature, S ₀ B. also "at 40 to 50 ⁰ C" to complete the reaction and when using less reactive components, e.g. - For some isocyanates or polycarboxylic acids or their anhydrides, heating can sometimes be useful. It is also possible to convert the starting products in the melt and, if appropriate, then in - preferably phenolic - solvents.

The reaction can take place, for example, in solvents in which the claimed reaction products are insoluble, for example in ligroin, benzene, ToIiSoI ₉ XyIoI ₁ , chlorobenzene, nitrobenzene, cyclohexane, ethyl acetate, butyl acetate, or in those in which the reaction products are soluble , such as "in M, M ⁸ -dimethylformamide, NpN'-dimethylacetamide, dimethyl sulfoxide, N-methyl ° pyrrolidone, Μ, Μ ¹ _Ä N" -Hexaraethylphosphorsäuretriamid, phosphorus acid-tris-CdiBiethylaiald) ^ cyclohexanone ,. Isophorone ^ acetophenone, also in phenols with up to 10 carbon atoms, e.g. phenol ^ cresols xylenol. In addition to the solvents already mentioned, the products are also soluble in ketones such as acetone, methyl ethyl ketone and di = butyl ketone. "

-9 -

1 0 9 8 5 2/1923 - BAD

The resulting solutions of the polycondensation products can be used as such. By means of suitable precipitation agents, for example water, alcohols, aliphatic and / or aromatic hydrocarbons, the solutions && reaction pro-. products are deposited as mostly more or less strongly colored powders. The latter can, however, also be obtained by evaporating these solutions in suitable devices, for example in spray dryers.

It is also possible to prepare polymers in that the products prepared according to the invention which still contain polymerizable groups, for example the radicals -NH-COOR ^, -NH-CO-COOR ⁷ (hereinafter referred to as Q and Q ¹ ), - COOH, - C00R ^v , -COOR

TV ν V

and -N ^ CO, in which R and R have the meaning given above under R and can be identical or different, according to equation (7), in which the symbols mentioned above apply and η is an integer from 1 to 70, preferably 1 to 50 is to be polymerized. This can be the case if the monomeric reaction products obtained according to the invention are heated to 120 to 550 ° C., preferably to 280 to 450 ° C., be it in solution or in solvent-free form, in the molten or solid state. In the process, chemical-resistant, temperature-resistant, practically insoluble film-forming polymers are formed. If the reaction temperature is chosen to be so high, for example from 150 to 300 ^° C., the reaction of the end groups 0 and Q 'proceeds with sufficient speed. "Polymerization" is to be understood here as chain extension by addition and / or condensation. The polymers can be separated off by precipitation and filtration. They are light yellow to brownish powders, which surprisingly catfish can be easily soluble. They are deposited practically unchanged from such a solution by adding, for example, water, alcohol or the like. The compounds are thus obtained as a powder or as crystalline, for example also microcrystalline, substances.

Depending on the chosen reaction conditions, des claimed process produces more or less polymeric products

109852/1923

BATH ORIGINAL ¹⁰ '* \

(cf. formula Xl, in which η, for example, can be an integer from 1 to 70). As a rule, products are obtained with a molecular weight that is not yet so high, so that, contrary to expectations, the products have a relatively good solubility in the usual solvents which do not contain reactive protons ("apronisoh") ^ (e.g. dimethylfoamamide, N-methyl pyrrolidone * Dlmethylsulfoxyd »N» N ', te'' ^: -HesQUBathy'! ^ Osphoreäuro triamld) have. There are no © Sete? I®r! GkQi '© © »even 30 to 70 % © solutions in the vo
averaging in a certain way without the ©
is. The solutions remain
Do not tend to crystallize, "Bieea Elg © ns®Ste ££ © n allow, with particularly good processing rates, versatile use of the products manufactured according to the invention for the production of polymeric heterocyclic compounds", due to the high molecular weight s © ig @ a di © products Improvement of the formative «Elg © asetoffcen and © iae" high theniic stability " ₀ EJöofo ÄMsläSFfcung erfeSlt üsan to deia raeisten solvents unlöeliefee Polyneriaafce. © lese tsalöslieli ^ n Polyuerisates can be produced in a certain level be "this little" B _e in use for the production of such oheniaoli resistant "his Porrat®il © si beneficial.

The inventive unsetauag lcaim salt or take place without a catalyst. As Katalyaatoren, check are generally those which are also used in ander® "Reactions of Isöoyaaaten sitit compounds having reactive hydrogen atoms vewejadot, s ₀ B _o tertiary bases, How-amines, for example TFiättiylaiHin _f Trib" tylaiiin ₀ M * = Isobutylmorpholin, pyridine , N-Methylpiperidtai, NfN-Diiisethylanllin, TriäthylendiamiHi, also triphenylphoaphinj, Triiiorptolisiophospliiia or their quesiiache. More catalystoa aiad gj. Lithium "" methylate, lithium benzoate "sodium"! Fithylate _ß - Kaliü3i "= feQ2" t _e btitylat ■ as well as organic zinc compounds such as dibutylslsmoxyd tin stearate, dibutyltin glycolate, dbutylzlnadilaiajpate

109852/1923
BAD ORIÖIHAl

tin oxide, ferrocene [»Dicyolopentadtenyl-elaen- (Ili |, also Metal ohelates such as iron aoetylaoetonate, cobalt carbonate, respectively individually or combinations of such compounds,

Suitable QxaidsKureeeters are those corresponding formula VI des Formula sheet in which

H and R ^{v have} the meaning given above and r is an integer from 1 to 6

Suitable isocyanates are those according to & B formula VIIt * where R * has the meaning given above and s is an integer from 1 to 4.

The method is equally well suited for production symmetrically as well as asymmetrically constructed triketole raidazolidine compounds. This is possible, for example, when using a polycarboxylic acid according to the formula 3QtVIS (see Foreel sheet),

The thermal stability is particularly great for products old one low hydrogen content »but especially if there is no aliphatically or cycloaliphatically bound hydrogen in the hetero ring system. The films and slides that made the claimed Preliminary products are obtained, »are also leaned by ßtehr good elasticity properties. Your adhesion to metal surfaces 1st big.

The radical R in the oxaric acid esters is aromatic in nature, i. a carboylike or heterocyclic radical, preferably of aromatic character. For example, it can be phenyl, naphthyl, benzene-azophenyl, Benzothiazoly, phenyl, anthraquinonyl, pyridyl mean.

Suitable bifunctional radicals R of the bis-oxamic acid esters are, for example, those according to formulas XII to XV of the formula sheet, in which X = * -CH ₂ -, -0-, -S-, -SS-, -SO ₂ -, -N »N- , -NR ⁷¹¹ -, (-R ^VI1 is an aliphatic, cycloaliphatic or aromatic radical with up to 8 carbon atoms -), also ^ lphenylen-, dimethyldi- ^ Änthr-.,, Nonylen- ,, PyrJ.dylen- , QuinolyXene, thiophenylene

ORlQINAU 0

Means benzofurylene and N-methylcarbazolylene radicals. The radical R- can furthermore be sub «in one or more aromatic and / or heterocyclic nuclei or in the side chain one or more times. be substituted, provided that the substituents do not react with the isocyanates under the conditions claimed. These Sufostituenten can be alkyl- * alkoxy- * halogensIky1 »« ester, alkylketo-, (co-m) -ketoalkyl-, alkylsulfony! Groups each with 5 carbon atoms, where ra is an integer from 1 to 3 * like -CH ,, -C ₂ H ₅ , -OCH ,, -OC ₂ H ₅ , -CP-, -COOC ₂ H ₅₅ »CN _fl -COCH ,,, -SO ₂ CHy also nitro, cyano groups * halogen, in particular Be P, Cl, Br _s. Similarly, Tris and / or Tetrateisoxaidsäureester can be used on their own or in a mixture with the bis « oxamic acid esters ,

The radical R ^"1 in the isocyanates b © d @ ut © t a a" to tetravalent, such as a cycloaliphatic alipltetisotop ^ aro = matlschen or gemischten- aroiiatisch = aliphatic radical ait generally up to 20 _ΰ preferably up to 15 carbon atoms ,, z "B"

Biitylene, furthermore the remainder © gerali Poraeln XII and IHI ₀ where X means -CH ₉ - or -0- ^ soui © according to formulas MI to XIX of the PoPßielblatts «,

This can be put in © in ° or multiple ways 2J ₀ by at least eto © Alicyl «° _ß Altos: ^ = · ^ Halogenallcylgrupp® rait J @ tf © ils to su 5 C ^ Ätoaseiii, further nitro groups, halogen- in particular P _ß CIj , Br ₉ eg -CH * " _{-C 2} Heβ" OCH ^ ,, -OCgHcp CF ^, where several arosaatisohe RlngQ can be substituted by -CH ₂ -, -O =, = 8 », -S = S-, -SO ₀ -J, -CO- or -N = N- v © rbundQSi s © in can «

If monom @ r @ products are desired ^ taan ratodestQna monofiBikt ions Ilen reaction partner will use as starting product "I ₀ isoejanate or Mono-osaraidsMur © © stsr ₀ .

Two types are substituted in each radical. R " ⁵ but not more than 5 H = Atora © by such elements

- 15 -

109852/192 3rd BATH L

TV ν

R and R in the oxamic acid esters used are, for example, alkyl radicals with up to 6 carbon atoms, preferably -CHL, -C ₂ H ₅₁ -C ^ Hg, phenyl or phenyl radicals substituted with alkyl, for example the aforementioned groups.

Suitable trivalent and tetravalent isocyanates are, for example, 2,4,6-triisocyanato-toluene, 4,4 ', 4 ^M -triisoeyanato-tri-phenylmethane, 2,4,4'-trisocyanato-diphenylmethane, 2,2', 5, 5 ^t -Tetraisocyanato-diphenylmethane, also trivalent isocyanates of the formula XX (see FormeIblatt), which are accessible, for example, by addition of trimethylolpropane to toluene-dilsocyanate, an Ieocyanate of the formula XXi which can be prepared by reacting hexamethylene diisocyanate and water (see Foraelblatt) or isocyanates with up to four free isocyanate groups of the formula XXIi (see formula sheet), such as can be prepared, for example, in the reaction of toluene diisocyanate and hexamethylene diisocyanate.

The tri- and tetra-isooyanates can also do the same above have listed substituents such as the diisocyanates,

Instead of the free isocyanates, compounds which split off isocyanates can also be used, for example diphenylethane-4,4'- ^{bis (carbamic acid phenyl ester), disulnylethane-4,4 l} -bl8 (carbamic acid butyl ester) _J , diphenyl-4,4 ^r -bis (carbamic acid diethylamine5).

Suitable polycarboxylic acids and their anhydrides are, for example, isophthalic, bromoisophthalic-amino-isophthalic, trimellitic, pyromellitic, terephthalic, 2,5-dianlllnoterephthal-, 2,5-ditolululnoterephthal-, 4-aminonaphthal-, 4 , 4-methylenebisanthranil, Hemlmelüth, Melllth, Maleln, Fumar, Itacon «. _# Hexahydroterephthal-, Adipin-, Olutar-, Bernstein-, Sebacin ·,

109852/1923 ORIGINAL BATHROOM

Suberic acid, Tetrahydrofurant traoarbonsäur © © _s benzophenonetetracarboxylic acid, 1,4,5,8-NaphthaXiiktetracarbon-g Perylentetraoarbonsäure, Benzophenonhexacarbonsäuredilaoton further condensed Syst ra @ © _ß contain at least 2 carboxyl groups in the molecule, wi © sB "N, N '-Terephthaloyl- bis-glycine * M ₁₁ N '-Isophthaloyl ^ bis-glycine, BIscarboxyraethylamino-dlpfottnylissfetea (bsw. «dipH ^ nylEther ^ or di ~

phenyleulfoss).

XXVIIa (see form ©! Sheet)

Suitable "polyoarbonaliiren siad au @ h ÄülngruppQii © Etlialtead © poly carboxylic acids, 'S ₄ B ₀ AmIdSJaUs ⁰ SSi _1)" wio they aniinodiphenylsulfon dMFQli UasQtgirag ψ © β f "felQin ° anhydride with DiaminodlphQga ^ SaQfete ^ p Diasain © diphQssy läthQF ₀ Si , p-Phenylendiaula od © pa »Ph © narl © sad £ aiii2i with amide formation and liberation of a capboscyl group of maleic acid»

anhydrides have been obtained o

The yields of N ₉ N'-disiJitefeitislQft® ^ 2 ₀ k _D \ are generally high in the case of the present method

about go % der Ttee ^ ie «

It 1st also possible *, utas MoleteulsrgQwieht the erf indungsgeraäß Reaktionsprodukt® is produced by © © © ttiemlseh treatment b @ i temperatures from 200 to 550 ⁰ C, wrstigsweis © between 26o 48o MiÄ ° C to increase Nooh and thereby © © in extraordinarily ® Therao «stability and practiced üalSliöM <© it la d @ a tibllehen means to achieve.

The inventions manufacTured, especially the nlederwolelculaf, can be used in a variety of ways, z _ffl B _o aiad si © organlsoh® syntheses. she

kularen form "- as a starting pointfcejflaliQii füb? di © pharmacist IkI ₁ ScMdI iisgetefeispf wigeis it tola

Myociden and Baetericiden ^ feraep Plastics and preferably polymerizatIons

1OS85 BAD

The products and polymers produced by the method according to the invention are also particularly suitable for coating flat metal moldings such as wires, sheets, plates, tubes, preferably electrical conductors, regardless of whether they are applied in powder form or in solution. In the same way, however, they can also be applied to ceramic moldings. After the thermal polycondensation, well-adhering, even high-temperature-resistant, thermally stable coatings are obtained on these objects. The claimed compounds are also suitable, especially in powder form, after mixing with fillers, in particular of inorganic nature, for example mineral powders, glass powder, glass fibers, asbestos fibers, graphite, metal powders and chips, for the production of shaped bodies by the HelSprefl method. With these fillers, the products manufactured by erfiaduageg®mES germinate at high temperatures, for example * at 280 to 500 ° C, and high pressure, for example 50 to 5000 at, are processed to form bodies. Furthermore, they can be used to form crystal-clear sheets and films as well as fibers. By means of suitable measures, for example the addition of blowing agents, but possibly also those, since the alcohol released and the carbonic acid formed can also act as blowing agents, the products can be processed into foam-like material with high temperature resistance. The products obtained according to the invention are also suitable as stabilizers for polymeric products, in particular for polymerization and / or polycondensation resins. They can also with such polymers, .einschließ -..- lent the polymerization and / or Kondensatlonsh & rzen with heterocyclic groups, at temperatures from minus 10 to + 250 ⁰ C, preferably at from + 20 to 190 * C in solution Sclmelze or mixed in the solid phase and processed further to form bodies and / or coatings. Another area of application is the production of high-temperature-resistant foams, which are particularly important for insulation purposes;

1 0 91 5 2 / "\; 2 1 BATH

Examples

1) 6o5 ε (2.4 moles) of 4,4'-diisocyanato-diphenyl ether are in 92 ¹ * g N-methylpyrrolidone-cyclohexanone mixture (30:70 weight Jf) at 100 ⁰ C dissolved "After addition of 16 g Triethylamine 318.5 g (0.8 mol) of HjV-bis-Uthoxalylamino) diphenylmethane (= formula XXXII see formula sheet) are entered within one hour. The temperature of the mixture is kept between 10 and 10 ° C. by cooling. The viscosity increases towards the end of the addition. The mixture is then stirred at 100-110 ° C. for four hours. Then a solution of 76.8 g (0.4 mol) of trimellitic anhydride in 2 ¹ Jo g N-methylpyrrolidone is added dropwise at lo5 ° C within an hour. The viscosity of the clear reaction product increases further. Finally stirred at 100 ⁰ C until the COp elimination ended. This is the case after about two to four hours.

2154 g of a clear, red-brown, highly viscous polymer solution are obtained (solids content 46 Ϊ by weight). A Iron sheet coated with this solution shows a clear, orange-yellow coating after baking at 35o ° C.

2) 199 g of 4,4-bis (ethoxalylamino) -dipheny! Methane (0.5 mol) and 96 g (0 ^ 5 mol) of trimellitic anhydride with 5W g of N-methylpyrrolidone after the addition of 1 g of lithium benzoate and 5 ml of tri -n-butylamine heated to 120 ° C and entered within 30 minutes 250 g (1 mol) of iJ, 4'-diisocyanatodiphenylmethane. Finally, the mixture is stirred for four to six hours at 120 ^° C. until the _{elimination of CO 2 has ended.} After cooling, 1065 g of a clear, highly viscous polymer solution are obtained.

- 17 -

109852/1923 ORIGINAL BATHROOM *

3) 199 g (0.5 mol) of bis (ethoxalylaraino) diphenylmethane, 96 g (0.5 mol) of trimellitic anhydride, 1 g of lithium benzoate and 5 ß of triethylarain are dissolved in 670 g of N-methylpyrrolidone-dimethylformamide (weight ratio 1: 1) solved. After the mixture has been heated to 150 ^° C., 375 g (1.5 mol) of ^ '- diisocyanatodiphenylmethane are introduced within 120 minutes. After cooling to 110 ° C., the reaction mixture is stirred for four hours to end the condensation. After cooling, 1185 g of a tough, clear red-brown polymer solution are obtained.

¹ O 756 g (3 mol) of 4,4'-diisocyanato-diphenyl ^{ether are heated to 100 0 g in 115 1} J g of N-methylpyrrolidone-cyclohexanone-Qemisjsh (weight ratio 30:70) and after adding 20 ml of triethylamine within two hours 398 g (1 mol) of bis (ethoxalylamino) diphenylmethane entered. After 45 minutes, 16 l g (0.5 mol) of benzophenone tetraearboxylic acid dianhydride are added over the course of one hour with vigorous stirring. The viscosity increases very sharply. After stirring for three hours at 100-10 ° C., a clear, red-brown polymer solution is obtained. Yield: 2400 g (pest body content about 52Ϊ).

5) 398 g (1 mol) of bis-ethoxalylamino) diphenylmethane and 96 g (0.5 mol) of trimellitic anhydride are dissolved in 1000 g of N, N ¹ -dimethylformamide-cyclohexanone (weight ratio 40:60) at MO ⁰ C. After adding 15 ml of triethylamine and 1 g of xyihexyl titanate, 522 g of 2,4-tolylene diisocyanate are added dropwise so that the temperature does not exceed 50.degree. Then, two hours at 5O ⁰ C is stirred. There are 1890 g of a clear, viscous solution with about 50.

6) 13 * g (0.5 mol) of naphthalenetetracarboxylic acid dianhydride and 39-8.8 ■ (1 mol) of bis (ethoxalylamino) diphenylmethane are added in 1150 g of a Geraisches of N-methylpyrrolidone-dimethylsulfoxtd (weight ratio ^ 5: 55) at 100 ⁰ C dissolved and within three hours, 756 g of 4,4'-diisocyanatodiphenyl ether (3 mol) were introduced with vigorous stirring and in a protective gas atmosphere «

109852/1823

Finally, for two hours at 10O ⁰ C is stirred. 2390 g of a dark brown, acidic polymer solution are obtained * The viscosity of this solution is above 100,000 cP (at 20 ^° C.).

If you work in the same way © _s @ tst- but instead of 756 g. said diphenyl ether nanraehr 731 g (2 _x i vtol) of this Xthers and susätzlicb 15 »^ g (O ₀ I mol) of m ^ chlorophenyl isocyanate in a way, one obtains a polymer solution ralt a viscosity of only about 30,000 eP (at 20 ⁰ CK

7) 398 g (1 mol) of Bi8- & thoxalylamino) -diph <Bnyli & @ than and 188 g (0.5 mol) of 2.5 ~ Bi8- (toluidino) -terephthalic acid are in 1336 g of dimethylsulfoxide-N, N * -Dimethy Dissolved acetamide (ratio 1: 1), heated to 100 ° C and added 5 g of diazäbic-yclooctane as a catalyst. AnsshlieSenö be entered at 100-120 ⁰ C 750 g (3 moles) iigV-Diisoeyanauo-diphenylfflethan., With vigorous Viskosifeätsanstieg the reaction mixture turns deep red-brown. Afterwards "one hour at 110 ~ 120 ° C was re-boiled". 2630 g of a clear, foeofevisite-iron polymer solution are obtained.

8) 398 g (1 mol) 4 _a U * -Bis- (ethoxalyl) -dipheny! Methane and 106.5 S (0.5 mol) li-ramino-naphthalic anhydride are dissolved in 1026 g of N-methylpyrrolidone and, after adding 20 ml of triethylamine to 130 ⁰ C heated. Then 522 g (3 mol) of 2,4-tolylene diisocyanate are added dropwise within a 3fcund ©. Then sswei hours at 100 ⁰ C nachgerührfc "There are 2,035 g of a clear, brown polymer solution get."

9) 161 g (0, § moles) benssophenonietpaesrbonstaredianhydpid 398 g (1 mole) M ^s -Bi3

in 1081 N-Methylpyrpoliidon g at IQQ ⁰ C dissolved Mnu 10 ml Tri benzylamine ssugegeben "Within örei hours w @ Fä © n 522 (3 moles) of 2, M-Toluylendiisoe ^ SNAT bai 12O-l4O ° C sugefcpopft" completion of Rsalitiöw SWEi Stunden'bei is nachgerührfe 100 ⁰ C. It is 2100 g © ipef
Polymer solution

BATH

10) 199 E (0.5 mol) 1 », 4 ^ BiS- (ethoxalylamino) -diphenylmethane and 250 g (1 mol) 4.4 ^l -diisocyanato-diphenylmethane are in 511 g of N-methylpyrrolidone-cyclohexanone (weight ratio 30: 70) at 100 ^° C. After adding 10 ml of triethylamine, the reaction mixture warms to 135.degree. The mixture is stirred for a further two hours at 100 ^° C., the viscosity of the solution increasing sharply. Then 62 g (0.25 mol) of tetrahydrofuran tetracarboxylic acid, dissolved in 186 g of N-methylpyrrolidone, are added dropwise over the course of 10 minutes. Until the end of C0 ₂ elimination is stirred at 100 ⁰ C. 1190 g of a clear polymer solution are obtained.

11) 796 g (2 mol) M'-bis-iathoxalylaminoJ-diphenylraethan and 756 g (3 mol) of 4,4-diisocyanato diphenyl ^r are dissolved in 1,000 ml of N-methylpyrrolidone and heated to 80 ⁰ C. ^{The temperature rises to 143 °} C. as a result of the exothermic reaction that sets in. After the reaction is at 130 ⁰ C 140 g (0.5 mol) Ν, Ν'-terephthaloyl-bie-glycine, dissolved in 692 g N-Methylpyrrolidonj added within one hour. Finally the mixture is subsequently stirred at 130.degree. C. for four hours. Yield: 3340 g.

12) 796 g (2 mol) 4,4-bis (ethoxalylamino) -dipheny! Methane and 140 g (0.5 mol) Ν, Ν'-terephthaloyl-bis-glycine are added to 1,000 ml of N-methylpyrrolidone dissolved by 20 ml of triethylamine at 100 ⁰ C. After stirring at einetündigea IQO ⁰ C a solution of 756 g is C 3 mole) of 4,4'-diisocyanato-diphenyl ether in 692 g N-methylpyrrolidone added over 30 minutes. The temperature rises to 106-1O8 ° C. Ea is stirred at 100 ^° C. for a further four hours. Yield: 3335 g of a clear, red-brown, viscous solution which shows greenish fluoro-essence.

13) 272 g (0.5 mol) 4,4 * -Bia- (4 ~ carboxy-phthalimido) -diphenylaethan'and 199 β (0.5 mol) ^ '- bis-utoxalylamino-diphenylmethane are in 1040 g M- Methylpynwlidon to 120 ⁰ C heated sugegeben 5 nl tributylamine and over 90 minutes 375 g (1.5 mol) of 4.4 x -Diieocyanato-dipheny! methane added. Fine crystals separate from the originally clear solution.

10985 2/19 23

BAD QRJOiNAL. . _;

Then is condensed at 190-198 ⁰ C until the now fully clear, viscous reaction mixture at room temperature, a clear, viscous polymer solution obtained. This is the case after about eight to ten hours. Yield: 1790 g of a clear, highly viscous polymer solution.

14) 213 E (0.5 mole) of 4,4'-bis (äthoxalylamino) -3,3'-dimethyldiphenylmethane (melting point 136 ⁰ C) and 250 g (1 mole) of 4,4'-diisocyanato-diphenylmethane are in 800 g of dimethylformamide at 8O ⁰ C. After adding 1.0 g of n-butyl titanate and 5 ml of tributylamine, the temperature rises to 92-95 ° C. as a result of an exothermic reaction. After two hours of stirring, the temperature is increased to 160 ° C. and 57.6 g (0.3 mol) of trimellitic anhydride entered within 30 minutes. Finally, stirring is continued for six hours at this temperature. After cooling, 1290 g of a clear, viscous polymer solution are obtained.

15) 98.4 g (0.2 mol) of crude 1, 4-bis (p-ethoxalylaminophenoxy) benzene (melting point 165 ° C.) and 19 _S 2 g (0.1 mol) of trimellitic anhydride in 100 ml dimethylacetamide at 130 ⁰ C and treated with 0.5 ml tribenzylamine. Within one hour, a mixture of Ί?, 5 g (0.15 mol) 11, ^1- diisocyanatodipheny! Methane and 45.4 g (0.18 mol) 4,4'-diisocyanatodiphenyl ether is introduced . Finally, it is stirred for four hours at l40 ° C, cooled to 70 ⁰ C and stirred in 100 g of technical-cresol mixture. After cooling to room temperature, 402 g of clear ₃ highly viscous polymer solution are obtained, the content of which is about 50 % pest body »

16) A mixture of 199 g (0.5 mol) 4 ₉ .4 '-bis- (äthoxalylamino) diphenylmethane (melting point 148 ⁰ C), 200 g (0.5 mol) of 4 _s 4 ^f bis- (äthoxalylamino ) -diphenylather (melting point 140 ⁰ C) and 10.9 g Pyrromellithsäuredianhydrxd (0.05 mol) are dissolved in 750 g whore thylsulfoxyd-N-methylpyrrolidone mixture (weight ratio 70:30) at 70 ⁰ C. After addition of 5 g of triethylamine and 0.05 g of lithium benzoate, 325 g (1.3 mol) of 4,4'-diisocyanatodiphenyl ether are introduced within two hours. The tem-

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109852/1923

BATH ORIGINAL

The temperature rises to around 90 ° C. After stirring for three hours at 80-90 ° C., the mixture is cooled to room temperature. 1465 g of a clear, red-brown, highly viscous polymer solution are obtained, the content of pest bodies of which is about 49 % .

17) 1,000 g of the polymer solution prepared according to Example 16 are mixed with 3,000 ml of ethyl alcohol at 60 ° C. with vigorous stirring dropped in within three hours. The one doing it The pale yellow polymer body which separates out is filtered off with suction after the precipitation has ended, with 1,000 ml of an ethanol-toluene mixture (Weight ratio 1: 1) washed and dried at 100 C in a vacuum. There are 475 g of a loose, pale yellowish Polyraeren powder obtained whose softening range is 14O-150 ° C.

- 22 -

109852/1923

Claims (1)

Claims 1. A process for the preparation of modified N, N'-substituted 2,4,5-triketoimidazolidines with reaction of alkyl oxamides with isocyanates or compounds which split off isocyanates, the oxamates having a grouping -NH-CO-CO-OR ^V , in which R is a aliphatic Iüalmliuwasserstoffrest with up to 18, preferably up to 6 carbon atoms, a cycloaliphatic teejügriswasserstoffrest with up to 8 carbon atoms, a mononuclear aromatic hydrocarbon radical, which can optionally be substituted with hydrocarbon radicals with up to I ^ carbon atoms, means - im generally at temperatures from -20 to + 280 ° C. and optionally in the presence of a catalyst, characterized in that polycarboxylic acids are additionally reacted with the formation of condensation products with amide and / or imide groups. 2. The method according to claim 1, characterized in that the reaction with the polycarboxylic acids takes place during and / or after the reaction of the oxamic acid esters with the isocyanates. 3. The method according to claim 1 or 2, characterized in that oxaric acid esters of the formula VII, isocyanates of the formula VIII and polycarboxylic acids of the formula Rpoly (COOH) are reacted, in which R is a mono- or polynuclear mono- to hexavalent aromatic or heteroaromatic radical with up to 20 carbon atoms, which optionally by halogen, nitro, dialkylamino, diarylamino, alkylaryamino groups, Alkyl, alkoxy, carboxyalkyl, carboxyaryl, acyl, e.g. acetyl, cycloalkyl groups or halogenated alkyl, Alkoxy-, carboxyalkyl-, carboxyaryl-, acyl-, e.g. acyl-j, Cycloalkyl groups, all of which are substituted by up to 18 carbon atoms, whereby the aromatic radicals can also be quinones, - 23 1 09852/1 9.23 ■ .ν '"'. ■ - if R is bound to an oxamic acid ester residue or if this ester radical is zero and polyvalent aromatic radicals can be linked to one another by aliphatic radicals or by heteroatoms, R is an aliphatic hydrocarbon radical with up to 18, preferably up to 6 carbon atoms, cycloaliphatic hydrocarbon radical with up to 8 carbon atoms, mononuclear aromatic hydrocarbon radical with 6 carbon atoms, optionally with - preferably aliphatic - hydrocarbon radicals with up to 14 carbon atoms Atoms is substituted,
r is an integer from 1 to 6, R "'has the meaning given under R or an aliphatic hydrocarbon radical with up to 18 carbon atoms or a cycloaliphatic radical Hydrocarbon radical with up to 12 carbon atoms means and s is an integer from 1 to H ,
^R Iy denotes a bivalent or trivalent, optionally substituted by halogen or amino groups, aliphatic, carbo- or heterocyclic, mono- or polynuclear, eg * cycloaliphatic, aliphatic-aromatic or aromatic hydrocarbon radical with two to 20 carbon atoms, <£ f- \ whereupon the formed products containing polymerizable groups are optionally polymerized. Yy. Process according to claims 1 to 3, characterized in that da & the molar ratio of the oxamic acid esters to the polycarboxylic acids 0.97 to 0.03: 0.03 to 0.97, the sum of the two compounds always being one mole. i «WM 109852/19 23
BAD ORIGiNAi. 5. The method according to claims l to 1 _fl, characterized in that the Änssahl of the oxamic acid ester and isocyanate groups in each case 2 to H and the number of carboxyl groups of the polycarboxylic acids 2 to 6 is ο 6. Process according to Claims 1 to 5 »characterized in that that the implementation feniÄ-ifeiBp «^ is carried out in the presence of solvents and / or catalysts » 7. The method according to claims 1 to 6, characterized in that the reaction is carried out in the presence of an amine ₉ phosphine _{s of} an alcoholate or an organic tin or lithium compound or mixtures of these compounds ο 8. The method according to claims 1 to 7 »characterized in that the polymerization by heating the monomeric compounds obtained in the first stage ax at least one? End group Q and Q ¹ to 200 to 550 ° € in solid form o <ä @ g> in the presence of solvents takes place »where Q and Q" have the meaning given above. 9. The method according to claims 1 to 8 ₉ thereby marked · = ·. draws that triraellite acid anhydride is used as a polycarboxylic acid. 10. The method according to claims 1 to 9® records that ¹ J ₉ 4'-diisoeyanato-dipheny! methane is used as the isocyanate. 11. Procedure according to tests 1 to 10 ,. thereby gelcennseichnet that 4,4 * -Bis · * (ethoxalylanino) -diphenylmethane is used as the oxamic acid ester. - 25 - 109852/1923 BATH ORIGINAL 12. Use of the according to the method according to claims 1 to 11 manufactured products for the production of moldings and coatings. 13. Use according to claim 12 for the production of moldings containing mineral fillers, preferably glass fibers and / or graphite. June 12, 1970
Dr. LG / Kr 109852/1923 1 H δι C-C A-NH-C-C-OIf * 2 I .1 r ^v ooc »co ~ nh-hm; (3) η (I) -) 2nR ^V 0H \ l-H. K η * 1 - 70 CO ♦ O = CsM- CO CU) ♦ B ^IV OOC-CO-NH-R-NH-CQ-eOOR ^V co, co «co _v ° \ R _tr -CQ-NH "R ^MS " M ^ I CO 'CQ Amide (III) TriketoiMidaaolidin-iaid (V) 109852/1923 / 2 co o \ co (6) O = C = NR "'- N = C = O + OR _tr -CO -., - * O = C = NR ^w ' -N _t R ^ -CO- ... (II) CO ^ ( V) Iffiid (VI) \ x / R ¹⁷ O-CO-CO-NH-RN CO-CO _y CO CO-CO _n ^ ^ NR "'-NH-CO-R ^,'NR" * -Ν _χ ^% -R ^fM -NH-CO-OR ^V -) (nR ^IV -0H + η R ^V -OH) (X) R ^IV 0-CO-CO-NH-R CO-CO CO K N-R "'- NH-CO-R, tr CO ' CO-CO t-j / N CO | n -R " ¹ -HH-CO-OR (XI) R- (NH-CO-CO-OR ^Y ) _r (VII) (VIII) . CO-CO QRN _n 'N - R " ¹ - Q ¹ CO " (IX) χ ^λ , (XII) (XIII) (XIV) (XV) 10985 2/192? / 3 (XVI) Xh) ■ _H _ ί CH, 2030233 CH,
I. H, C H ₃ C -CH ₂ -C-CH ₂ - -CH-CH ₂ -CH ₂ - (XVII) CH, HjC (XVIII) (XIX) NCO CH.-CH «- -C - CH - O - CO - NH - O - CO - NH CH ₂ - O - CO - NH NCO (XX) i- NH - - (CH ₂ ) ₆ - ν; NCO X - NH - '(CH ₂ ) g - NCO 0 (XXI) NCO NCO (XXII) 1: 09852/192 HOOC ν - ■ χ - ν: COOH (XXIV) HO-I HO - ' ^ou .ΛΑ (XXV) C-OH HOOC HOOC Ii C - ir S ⁰ " (XXVI) HOOC COOH COOH (XXVII) (CH ₂ ) _m , Μ = 2 - CH, SO (XXVIia) 109852/192 3 / NHC - Y - C - NH (XXVIIIa) CO-CO CO CO-CO ν N co-co Ϊ CO "poly R »f - Qi (XXIX) O O Lc Q-R-N N - f - - Q ¹ (XXX) / 6 109852/1923 R ¹ - (kV , / poly CO CO CO co (XXXI) - (CgH * - NH - CO - COOC ₂ H (XXXII) Q- R - Q '+ R " ¹ Q - n N = C = O) ₂ CO - CO I " co N - R " ¹ - Q (XXXIII) 109852/1923 BATH ORIGINAL