DE1920845A1 - Process for the preparation of disubstituted 2,4,5-triketo-imidazolidines - Google Patents

Description

REICHHOLD-ALBERT-CHEMIE AG, 2 HAMBURG 13, IVERSSTRASSE

Patent application ₍

Process for the preparation of dl-substituted 2,4, ^f y-trlketo-imidazolldynes

It has already been proposed to react OxamidaHurealkylester with isocyanates to form N, N'-substituted 2,4, '.-Triketo imidazolidinen. The implementation can take place according to the following equation: · _QQ

OO _/ CC

(1) A-NH-CC-OR + 2 BN = C = O r AN 'NB + B-NH-C-OR

The second mole of isocyanate is used as a condensing agent at. the formation of the imidazolidine ring.

Ea has now been found that bis-oxamic acid esters of the formula

(D

ROOC-C-NH-A • -NH-C-COOR

r «

0 0

with isocyanates of the sleeve

(II) B »- (N = C = O) _x

R is an alkyl radical with up to 6 carbon atoms, A 'optionally one substituted divalent cyclic, preferably aromatic radical with up to 12 carbon atoms each in the Rinßsystem, where a core is substituted up to 4 times can be,

_N finpn . '
B'Vifunctionally one to three times substituted two-

to tetravalent radical having up to 20 carbon atoms, and χ is an integer from 2 to 4 yon
mean to compounds of the formula

009845 / 1-905.; ^Bm

O O C C

RO-CC- NH -r- A »-1 -Β» -1

(III)

ο ο

\ j ^m "■""""ν

I! O - «- NH - C - OR

it O

-B ¹ - R

9 "

■ ve-

Il

or

ο ο

- N

ν 0

i;
ί Ε
I.
t- - »■ - I. ρ— r "ft 4 I.
j I |
O I ■ · Ä "■■ ■ [ i O
ll
! «
p—
n '
G-
I. f - {
α 1
1 1
i O
c— S. -C O
M. Ό
Π
-σ

ill

■ r , _t «...

_N .A »

in

(V)

ι. _

BAD ORfQINAL

1 *; ^ Γί - ^

are reacted, in which R, A * and B ^{1 have} the above meaning, η is an integer from 1 to 50 and y is 1 or 2, whereupon the products containing polymerizable groups are optionally polymerized. The compounds V can therefore be branched, the branching point being contained in the remainder B *. “Polymerization” is to be understood as meaning chain extension by addition and / or condensation.

This gives products with a relatively low degree of polymerization. In this reaction, for example Analogously to 1 mol of bis-oxamic acid ester with one mol of diisooyanate Equation (1) react, but only one isoyanate group is used for ring formation, while the other plays the role of Condensation agent takes over. This reaction proceeds according to the equation *.

0 0 0 0

RO-C-C-NH-A • -NH-C-C-OR + O = C = N-B '-N «C * = O

(2) ■. ■ |! f

0 0 _/ CC 0

? RO-CC-NH-A »-N ^ .NB · -NH-C-OR (compound X)

In addition, multiple forms of the compound X can also arise, e.g.

oo ο ο 9-9 ο ο cc ₇ cc, σ- σ ο

RO-CC-NH-A'-N .N-B'-N "Ν-Α · -Ν .NB ¹ -NH-C-OR + 2 ROH

I! · Il II

0 0 0

Common to all are the end groups

0 0 0

.! ι l ·

RO-C-C-NH- or -NH-C-OR.

Furthermore, the reaction of bis-oxamic acid esters with di-

00984571905

isocyanates formally expect the following course:

0 0 0 0

η RO-CC-NH-A'-NH-CC-OR + 2n ^{O-OH-B 1} - NC = O

0 0 0 0 ~

> ■: ff il

C -C C- C 0 0

A »-N _v NB '-Ν! N- ~ - + η RO-C-NH-B'- -NH-C-OR

^ H ^ r in

0 0- (IV)

The I.R. spectroscopic examination of the reaction products obtained according to the invention clearly demonstrated the presence of --NHCOOR groups. In addition, there is also the characteristic grouping of bands ^{for the 2,4, C. -Triketoimidazolidine-}

CO-CO

■ CO

whereby the reaction according to equation (2) is hardened. What is certain is that in the process claimed, the polymers of equation (3) arise only to a small extent if the reaction conditions are correctly selected. They can be recognized by the fact that they contain no reactive protons in the usual solvents (= "aprotic") ) are insoluble. However ^{, the products obtained according to the claimed λ 7} are easily dissolved in such solvents

009845/1905

BAD OFUGiNAL

Difficult even 3O-6c # solutions in the above win aprotic solvents without the viscosity of the same is very high. The solutions are stable in storage and do not tend to crystallize. These properties allow versatile use of those produced according to the invention Products for the production of polymeric heterocyclic compounds.

Namely V / ground reaction products according to the invention, be it in solution or in solvent-free form, in the molten or solid state, to 120- ^ 50 ⁰ C, preferably at 280- ^ ^P 0 ° C, is heated, the end groups react the same in accordance with the following equation with the formation of practically insoluble, chemical-resistant, temperature-resistant, film-forming polymers:

⁰ °
0 0 CC 0

η RO-C-C-NH-A '-N N-B' -NH-C-OR - 2n R-OH

0 0 0 0;

!; I ₁ | l I

C C C Ό j

Α · -Ν " ^V NB '-N ^ .'Ν —t- (IV)

ο ο in

In the compounds IV and V, the same radicals can be used as in the compound III form the end groups. But it is also possible that oxamic acid ester groups, or these ester groups, are seldom on both only on one side and on the other side Urethane or isocyanate residues or methane or isocyanate residues on both sides are arranged,

The implementation according to equation (**) represents a condensation. during reaction (j5) an addition, followed by a Kordenaa 11 ο π, ν Gx ^s a eis ü ha ι = 11 ο h t.

υ y 0 ν η sJ / ι «υ sj

1320845

The high chemical uniformity of the polymers obtained can be recognized by the extraordinary tendency towards film and foil formation. The thermal stability is due to the low content to hydrogen, but in particular favored by the lack of aliphatically or cycloaliphatically bound hydrogen in the polymer. The films and foils that are obtained from the claimed preliminary products are also characterized by very good elastic properties. Their adhesion to metal surfaces is great.

Suitable bifunctional radicals A »of the bis-oxamic acid esters are aromatic and / or heterocyclic radicals, e.g .:

Vx- /

where X ä is -CH ₂ -, -0-, -S-, -SS-, -SQ ₂ -, -N = N-, furthermore pyridylene, quinolylene, thiophenylene, benzofurylene and N-methylcarbazolylene radicals, those in one or more aromatic and / or heterocyclic nuclei one or more times, for example by alkyl, alkoxy, haloalkyl, ester, alkylketo, (4 / - m) -ketoalkyl, alkylsulfonyl groups each having 5 carbon atoms * where m is an integer from 1 to 3, such as CH ₃ , -C _s H _{r 9} -OCH ₅ S -OCgHp-, CF ₃ , -COOC ₈ H,., -CN, -GOCH ₈ , -SO ₂ CK ₃ , also nitro, oyan groups, halogen, in particular F, Cl, Br, can be substituted.

The radical B ¹ in the isocyanates denotes a bivalent to tetravalent, preferably a bifunctional, aliphatic, cycloaliphatic, aromatic or mixed aromatic, aliphatic radical with generally up to 20, preferably up to 15, carbon atoms, e.g.

Propylene, butylene,

00SS4 5/190

CH ₈

Alkoxy -jtJ-, for example, by at least one alkyl group with up to 5 carbon atoms each, also nitro group / halogen, in particular F, Cl, Br, e.g. -CH ₈ , -C ₈ H ₅ , -OCH ₈ , - OCgH ₅ , CF ₈ can be substituted, whereby several aromatic rings can be connected by -CH ₂ ~ s -0 * ·, -S-, -SS-, -SO ₈ -, CO- or -N »N ~. ",

Suitable trivalent and tetravalent isocyanates are, for example, 2,4,6-triisooyanato-toluene, H _s k *, b * • -Triisooyanato-triphenylmethane, 2, U, U »-triisocyanatio-diphenylmethane, 2,2 ♦, ^{c;, ;} ; '- Tetraisocyanatodiphenylmethane, also trivalent isocyanates of the formula

. NCO

CH ₂ - 0 '<* CO - NH- (Oh- ^CH »^ N CH _a CH ₈ - C-CH ₂ - 0 - CO - NH ~ / o \ ~ ^CH s ^) ( ^VI )

CH ₂ - 0 - CO - NH - (P) - CH ₈ '

V ^ C NCO

which are accessible, for example, by addition of trimethylolpropane to toluene diisocyanate, one by reaction isocyanate that can be produced from hexamethylene diisocyanate and water

_(vn)

or isocyanates with up to four free isocyanate groups formula

the formula - (CH ₈ ) ₆ -N 0
Il - NH (CH ₂ > 6- NCO Ii
C. OCN - NH (CH ₂ > 6 ~ NCO ^x c
Il 0

ο N ^ H ^ "NN ^NC0

<o Il from left

0 CH ₈ CH ₃

as e.g. from the reaction of toluene diisocyanate and Hexamethylene disocyanate can be produced.

The tri- and tetraisooyanates can also do the same above Have listed substituents such as the diisocyanates.

The bis-oxamic acid esters are generally reacted with the diisocyanates in a molar ratio of I0.8-2.2, preferably IiO.9-1.5. The reaction can take place in the melt, but especially in the presence of solvents. The reaction can, for example, 1.) take place in solvents in which the claimed reaction products are insoluble, for example in ligroin, benzene, toluene, xylene, chlorobenzene, or 2.) also in those in which the reaction products are soluble, such as in N. , N ¹ -dimethylformamide, N, N'-Dimethylaoetamid, dimethyl sulfoxide, N-Methyfcyrrolidon, NiNSN'-Hexanjethylphosphorsäuretriamid, cyclohexanone, isophorone, acetophenone. In the first case the desired reaction products are obtained as filterable solids, in the second case as more or less viscous solutions. Of course, if required, a mixture of the solvents mentioned under 1. and 2. can also be used. The reaction according to the invention can be carried out with or without catalysts. Suitable catalysts are in principle those which are also used in other reactions of isocyanates with compounds with reactive hydrogen atoms, for example tertiary amines, organic tin, iron, cobalt compounds, tertiary phosphines or mixtures or complex compounds thereof or combinations of such compounds, the inventive reaction may proceed at temperatures of "10 ° C to + 28O ⁰ C ⁹ to C l8o ° C be carried out at O, preferably. If the reaction temperature is chosen to be so high, for example from IfO to j500 ° C, that the end groups are converted

0 0 0. ■

-NH-C-C-OR and -NH-C-OR with sufficient speed. Runs * so in some cases also: in the aforementioned ©]! apyotisoh @ n solvents insoluble polymers can be obtained .. you can also separated by filtration. Si © put bright » yellow to brownish powders, which mostly consist of concentrated sulfuric acid are soluble. From this solution.

009845/1905

BM) ORIGINAL

they are practically unchanged by adding e.g. water deposited.

The claimed compounds fall as powders or microcrystalline Substances which, in addition to the solvents already mentioned, are also found in ketones such as acetone, methyl ethyl ketone, Dibutyl ketone, and soluble in phenols such as phenol, cresol, xylenol are. .

The products manufactured according to the process according to the invention and polymers are particularly suitable for coating metallic moldings such as wires, sheets, plates, tubes, It does not matter whether the application is in powder form or in solution, but they can also be applied in the same way ceramic moldings are applied. After the thermal polycondensation, well-adhering, thermostable coatings obtained - the claimed compounds but are also suitable, especially in powder form, naoh ver mix with fillers, e.g. glass powder, glass fibers, asbestos fibers, Metal powders and chips for the production of shaped bodies after the hot pressing process. Furthermore, they can be made crystal clear Sheets and films are molded. Appropriate measures, e.g. Adding propellants, sioh the products to foam-like Process material with excellent temperature resistance. The products obtained according to the invention are also suitable as stabilizers for polymeric products, especially for polymerisation and / or polycondensation resins.

Example 1 .

398 g (1 mol) B6-N, N'-ethoxalyl - ^, ^ '- dlamino-diphenylmethftn are first with 2f, 2 g (1 mol) ^ «- Dl-isocyanato-diphenyl ether in 2 * above N, N • -Dimethylformamide and iäOO g of N-methylpyrrolldine stirred for one hour at room temperature under protective gas (^ ₃ or CO ₈ ). Then a solution of 10 ml of triethylamine and 0.3 g of cobalt naphthenate in ^K 0 ml of N, N • -dimethylformamide is added dropwise so that the temperature does not exceed ^e 0 ^{e C.} Nachgerühmt Na'ch the exothermic reaction ^ n iTU © oh uvQi hours. Ee a light yellow solution is obtained, dl © one

009845/1905

Has a viscosity of 1200-1300 cP (20 ° C). If Bleohe are coated with this solution in the known way and the layer is baked for v minutes at 375 ° C, one obtains clear, elastic, well-adhering coatings with excellent Solvent and chemical resistant.

Example 2

308 g (1 mol) 1,1 "-Dl -ethoxalylamino -benzene are mixed with 250 g (1 mol) 4,4" -di-isocyanato-diphenylmethane in 400 g N, N'-dimethylaoetamide and 1 ^c 8g Ntff, Dissolved N ¹ '-hexamethylphosphoric triamide at room temperature and added 5 ml of triethylamine. The temperature rises to about 70 ^e c. The initially low-viscosity liquid gradually becomes more viscous. After the exothermic reaction has subsided, stirring is continued for 2 hours at 80 ° C. The final viscosity of the solution is given. . ;

2000-2500 CP (20 ° C).

With this solution, coated copper wires provide after a 160-second thermal treatment at 43o C ⁰ clear, well-adhering coatings with high chemical and thermal resistance.

Example 3 "

384 g (1 mol) 4,4-Dl-ethoxalylamino-diphenyl and 202 ¹ g (1.2 MqI) 1,6-Di-Isocyj «iato-hexane with 5 g N-Methylmorpholine and 0, fg iron acetylacetonate one hour kept at 150 ^° C. for a long time, then 293 β dimethyl sulfoxide are stirred in and the mixture is stirred at 100 ^° C. for a further 4 hours.

The light brown solution provides on metal surfaces in the thermal treatment at 240 ° C clear, light ^brown; elastic covers.

Example 4

400 g (1 mol) of 4,4 ', "Di-äthoxalylamino-diphenyläth®F and 174 g (1 mole) of tolylene-2,4-diisooyanat are stirred at 5O ⁰ C,

009845/1905

/1

1820845

Then 3 ml of tri-n-butylamine are added. Duron cooling ensures that the temperature does not exceed ^{8o e.} Then 574 g of N-methylpyrrolidone are added rapidly. After 5 hours at 7Ö-8O ° C with stirring, a clear, pale yellow solution of medium viscosity (cP I5OO-I8OO 2O ⁰ C) is obtained. This solution is clear when baked on unglazed earthenware at 42O ⁰ C, orange-brown, well adhering coatings of high thermal stability,

Example 5

412 g (1 mol) ^ il ^ -Di-ethoxalylamino - ^^ - dimethyldiphenyl and 2 ^r 2 g (1.2 mol) naphthylene-1,5-diisocyanate are mixed with l ^r 0 g cyclohexanone and 6 ^ 0 g N- Methylpyrrolidone at 50 ⁰ C stirred homogeneously. After addition of 0.5 g and 2 g of triphenylphosphine Dibutylzinnglykolat the temperature is raised to l80 ^e C. The initially cloudy reaction mass becomes almost clear in the course of 4 hours. It is filtered through a pressure filter, after which a clear, orange-yellow solution is obtained. When this solution is stoved on glass plates at j575 ^e C, ^ lare, hard films are obtained,

Example 6

444 g (1 mol) of 4,4-diethoxalylainino-; 3,3-dlmethoxy-diphenyl are dissolved in 100 g of N, N'-dimethylaniline and 700 g of N, N-diraethylformamide with stirring. Then, at 5O ⁰ C, a solution of 252 g (1 mol) of 4,4-di-isoeyanato-dlphenyläther in I50O ml of xylene is added and the temperature is raised to l4o ° C. The initially clear solution becomes cloudy and a pale yellow body begins to separate. After a few hours the mixture is cooled to room temperature, the body of the pest is filtered off, washed with toluene and dried in vacuo at 70 ° C.

Yield: - 622 g «89 % of theory. The light yellow powder obtained dissolves easily in N, N-dimethylacetamide, dimethyleulphoxide and N-methyipyrrolidoh. The solutions deliver on metallic surfaces when baked at 220 ^o C j55Q clear, elastic coatings that solve only more concentrated in warmed "sulfuric acid.

009846/1905

JH

Example 7

3θ8 g (.1 mol) of 1,3-di-ethoxalylamino-benzene are dissolved in 560 g of N-methyl-pyrrolidone at 3 ^ ⁰ C under nitrogen as a protective gas. 250 g (1 mol) of ^, A'-di-isocyanato-diphanylmethane are then stirred in. After good homogenization, 5 ml of triisopropylamine and 0.2 g of tris-carboxyethylphosphine are added. The temperature rises to about 70 ° C to * Now is stirred until the exothermic reaction subsides and the temperature dropped to 50 C ^01. The mixture is stirred at this temperature for a further 3 hours. The light yellow viscous solution in this form is suitable for coating metallic surfaces. The stoving can be done at 32 ° -30 ° C. The clear, brownish-yellow coatings are stable even at high temperatures. Loss of weight is at 400 ° C after 5 minutes in the air less than 3 # · The thermal endurance at 325 ⁰ C.in air is greater than 15 hours.

Example 6

322 g (1 mol) l ^ -di-ethoxalylamino- ^ - methyl-benzene and 279 g (1.6 mol) Toluylen- * 2, ii-? DlJsooyanat are at room temperature with 400 g of N-methylpyrrolidone and 50 g of isophorone are stirred and it 10 g of triethylamine are added. The temperature continues to rise the addition of the catalyst to about 50 ~ 60 ° C. That initially cloudy reaction mixture becomes clear. The reaction is if you can no heat supplied, terminated after stirring for 4 to 6 hours. The solution obtained can be used for the production of higher temperature resistant use exercises.

Example 9

^ 00 g (1 mol) 4,4'-Di-ethoxalylar «ino-aiphenyläth« r: 'become' with 2 ^F »2 g (1 mol) ii ^ '- Di ^ isooyana.toHdliphenylfithÄr uM 650 g -ϊί- Mefehyl * -. pyrrolidone b "ai room temperature stirred 2SU * ~ aw br # © iig ii Hisohuns be ν ml Trl-n-butylamine. The temperature rises to

009845/190 5

against 6o ° C. It is now stirred for 6 hours without adding heat. The clear, bräunlichgerbe solution thus obtained has a viscosity of about l4oo cP (20 ⁰ C) - Duroh baking this solution on glass plates at 356ö ° C during J50 minutes are obtained clear light brown films, the analysis of the elastic film gave the following values: ·.

found 64.67

22, Io % ΙΟ, οο jo

100.15 %

calculated

$ 64.28

£ 2.88

22.84 #

ΙΟ, οο ^

100.00 <f>

In the I.R. spectrum of the film there were neither urethane nor ester, -NH- groups still detectable.

Example Io

398 g (1 mol) of 4,4'-di-äthoxalylamJjino-diphenylniethan be N-methyl pyrrolidone dissolved in 800 g with the addition of 10 ml of triethylamine at 70 ⁰ C; In portions throw 500 g (2 mol) 4, ^ t-Diieocyanato-diphenylmethän added. The temperature should ^{not exceed 8o-8 p} . ° C. After the addition was complete a further 6 hours is stirred at room temperature and then with 100 g of a mixture of phenol and cresol (ratio Iji) diluted "There is obtained a clear, yellow solution at / n baking bei2 ^ 0-41O the ^- C on metallic Provides well-adhering film coatings on surfaces. -

Example 11

448 g (1 mol) of 4,4 »-Di-ä" thoxalylamino-diphenyl sulfone are with

00984BV1905

2f> 0 g of N, Ν », Ν ¹ · - hexamethylphosphoric acid trlamide and 450 g of N-methylpyrrolidone with the addition of 10 g of triethylenediamine stirred to a paste. Then, 252 g (1 mol) ^, ^ '- di-isocyanatodiphenyläther added so that the temperature of the Reaktlons-, mixture 60 ⁰ C exceeds nioht. The initially thin paste turns into a clear solution with moderate viscosity. The reaction is brought to the end by stirring for 8 hours. The solution obtained upon heating provides on metallic surfaces (10 Min.325 ⁰ C), clear films, which are extremely resistant to organic solvents.

009845/1905

Claims (1)

Pat e nt a ns pr tlch e 1. Process for the preparation of disubstituted 2,4, ketoimidazolldinen, characterized in that bis-oxamide acid esters of the formula (D ROOC- C - • NH. - A- * - NH - C - GOOR it 11 ■ 0 with isocyanates of the formula '■■' : (n) Bt - (N »C» O) _x wojjin; * " R is an alkyl radical with up to 6 carbon atoms, A * an optionally substituted divalent cyclisoheni is preferred aromatic residue with up to 12 carbon atoms in each case in the ring system, with a nucleus can be substituted up to Jj times, B 'one optionally one to three times. substituted bivalent to tetravalent ones The remainder with up to 20 carbon atoms and χ denotes an integer from 2 to b , to compounds of the formula 00984 5/19 05 1320845 ii C- RO - C - C - NH-A '-N r ι; '0 O O N-B '-N , (III) ο ο C C AT' or 0 N - B « - NH - C - OR C.
N ι:
0 0 0
I ₁ 0 0 ~ *
> 1'
-C
\
N - B. t _ C C
ν 'ν-- - C "
0 '' NS - '^
I '
0 (IV) or P- Et N - Α « in 0 | l i! , C C AT N - B '- N i! —C o -o - i \ ' Ii V C- C ι -; \ y N
^ c /
k N. - A (ν) 009845/1905 ■ reacted, where R, A 'and B »have the above meaning and η is an integer from 1 to ¹ O and y is 1 or 2, whereupon the products containing polymerizable groups are optionally polymerized. 2. The method according to claim 1, characterized in that the bis-oxaraidsäureester> .nd the diisocyanate with one another in the molar ratio Ij (0.8 to 2.2), preferably 1: (0.9 to 1 _f "5), are reacted . J>. Process according to Claim 1 or 2, characterized in that the reaction takes place in the presence of catalysts. 4. The method according to claims 1 to; 5, characterized in, that the reaction takes place at temperatures from -10 to 28o ° C. 5. Process according to Claims 1 to h, characterized in that the polymerization is carried out by heating the compounds III to 200 to ^ ¹ O ⁰ C in solid form or in the presence of solvents. 6. Compounds of the formula 00 0 0 υ i. "r. E- C-C, C-C RO-CG-NII 'A' - / ", N - B» -N, ' U ■■■ - j ■ 0 On (III) 0 0 ....- ■ · .. ..G C Λ »-N ^/ H - B * - NH -C- OR 9.- ' ■ Ό 0
where R, A », B» uiu η have the meaning given above. BAD ORlGiHAL 7. Compounds, the units of formulas O 0 , ¹ N -Β »- N - (IV) ο. .σ ■ - A '- N-. - B ' . ! I N χ ι. σ N. - N N / A" (V) contain, in which A ¹ , B ¹ , y and η have the above meaning. 8. Use of the compounds according to claims 6 or? to the Stabilization of polymer products. Q. Use of the compounds according to claims 6 or 7 for Manufacture of moldings and coatings. April 21 Dr LG / ma 009845/19