DE1720694C3 - Process for the preparation of polyhydantoins containing imide groups - Google Patents

Description

a) polyvalent glycine ester derivatives of the formulas

or

- C - C

N-H

HR ₁

N-C

or

in which R is an n-valent, aliphatic, aromatic or araliphatic radical, R is a hydrogen atom or an alkyl radical, R _{2 is} a hydroxyl, amino, alkylamino, dialkylamino, alkoxy or aroxy radical, R., a hydrogen atom or a Alkyl, aralkyl or aryl radical and η is an integer between 2 and 4, with

b) 105 to 180 ° / o of the equivalent amount of Diisocyanates or dithioisocyanates and

c) subsequent implementation with multifunctional compounds, optionally in Presence of 0.1 to 3% of a catalyst, based on the solids content, at temperatures from 100 to 300 ° C,

characterized in that compounds are used as multifunctional compounds with 2 or more cyclic anhydride radicals or with one cyclic anhydride radical and additional Hydroxyl, mercapto, carboxyl or amino radicals are used.

- C —C

N-H

R ₅

Process for the preparation of polyhydantoins have already been described, e.g. B. in the Belgian patent 678 282 or in Dutch patents 6,708,427 and 6,708,428. All of these Processes are based on the implementation of multivalent Glycine ester derivatives with polyisocyanates xler polyisothiocyanates to the polyureas in question, which are cyclized simultaneously or subsequently.

in which R is a / i-valent, aliphatic, aromatic or araliphatic Resi, R _{1 is} a hydrogen atom or an alkyl radical, R _{2 is} a hydroxyl, amino, alkylamino, dialkylamino, alkoxy or aroxy radical, R _{3 is} a hydrogen atom or a Alkyl, aralkyl or aryl radical and η is an integer between 2 and 4, with

b) 105 to 180 ⁰ Zo the equivalent amount of diisocyanates or dithioisocyanates and

c) subsequent reaction with polyfunctional compounds, optionally in the presence of 0.1 to 3 ⁰ Zo of a catalyst, based on the solids content, at temperatures of 100 to 300 ° C,

which is characterized by the fact that one is multifunctional Compounds Compounds with 2 or more cyclic anhydride residues or with one cyclic anhydride residue and additional Hydroxyl, mercapto, carboxyl or amino radicals are used.

The second reaction stage can immediately follow the first stage in the same vessel. Accordingly, the polyvalent ones used in the process according to the invention are converted into Glycine derivatives with diisocyanates or dithioisocyanates obtained oligonucleotide polyhydantoin plastics then immediately implemented with a compound in one process step, which in addition to a cyclic anhydride group still further hydroxyl, mercapto, carboxyl or Amino residues or even further cyclic anhydride groups contains.

The reaction should be shown schematically using the example of pyromellitic dianhydride as follows will.

i 720

R —NH-COOR + O '

/ ⁰⁰ VY ⁰⁰ N

I I

CO

CO O + RO —CO —NH-

CO

R-N

X /

co '■ -J

N-R + CO ₄ + RAW

The polyhydantoins produced according to the invention are excellently suited for producing high-temperature-resistant ones Lacquers.

The polycondensates obtained by the process according to the invention can also be used in a conventional manner Way in a 3rd stage by reacting polyalcohols, polyamines or amino alcohols with the existing carboxyl radicals are implemented.

The polyfunctional cyclic acid anhydride compounds used in the present invention derive z. B. from pyromellitic acid, trimellitic acid, mellitic acid, naphthalene-1,4,5,8-, Naphthalene-2,3,6,7- or naphthalene-1,2,5,6-tetracarboxylic acid, the diphenyl ether or diphenyl-3,3 ', 4,4'- and diphenyl ether or diphenyl ^^' ^^ '- tetracarboxylic acid, the 2,2-bis- (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxylphenyl) sulfone, perylene SAO.lO-tetracarboxylic acid, of ethylene tetracarboxylic acid.

The internal anhydrides of hydroxy, mercapto or amino-o-phthalic acids, of hydroxy, mercapto or aminonaphthalenedicarboxylic acids, whose carboxyl groups are in o-position to one another, may also be mentioned. For the purposes of the process according to the invention, bisadducts of maleic anhydride with styrene or substituted styrene are also suitable, as are phenylene-bis- [alkane-di- (carboxylic acid anhydrides)], as described in Belgian patent 613 374, as well as bicyclotetracarboxylic acid dianhydrides as described in US Pat. No. 3,037,966, and by chlorination of paraffins in the presence of e.g. B. maleic anhydride obtained polyanhydrides.

The compounds used as anhydride component can also be more or less polymeric Be natural, for example, bistrimellitic anhydride esters of the structural formula can also be used here

O:

- CO-O-R-O-CO- ! O

be used.

R therein denotes a saturated or unsaturated aliphatic or cycloaliphatic divalent one Rest in which aromatic, cycloaliphatic or heterocyclic ring systems as well as ether, ester,

- (CH ₂ ),

- (CHJ ₄ -, - (CHJ ₈ -, -

CH, -

Sulphide, sulphoxide or sulphone bridges may be incorporated can and which is optionally substituted by chlorine, bromine, iodine, a nitro, alkoxy or mercapto group can be.

Examples for R are:

- CH ₂ - CH ₂ - O - ,;

- O —CH ₂ , -CH ₂

• CH ₂ -,

- (CHJ ₁ - O - (CHJ ₁ -, - (CHJ ₂ -S - (CHJ ₂ -, -CH, -

; -CH ₂ -,

Cl

CH ₂ CI

CH ₃

CH ₂

-CH ₂ -, -CH ₂ -CH-, -CH ₂ -CH = CH-CH ₂ -, -CH ₂ -C = C-CH ₂ -

H H

- CH ₂ - CH ₂ - O - C -

> - C - O - CH, - CH ₂ -

In general, the amount of anhydride is also determined by the diameter of the

adjust so that one of the excess iso the wire a role. The by the paint job too

cyanate corresponding amount of anhydride used; reaching diameter increases of the wire

this then leads to the imide groups in the poly- are in DIN regulations 46453 and 46435

hydantoin. 5 established. A higher viscosity solution or a

On the other hand, the anhydride solution used can have a higher solids content Components also in excess or shortfall, usually deposited by means of metallic wiper nozzles and then in a well-known way in striped.

Additional ester, amide and imide groups are then produced. The wire then passes through a stoving furnace,

holding plastics are converted. io in which the solvent is consumed by the action of heat

According to a further variation, under vaporization takes place and the curing of the lacquer film causes under conditions a reaction with hydroxyl acid. This process is repeated several times until the required layer thickness is reached, or cyclic compounds containing carboxyl groups. Mostly hydrides. These react with their anhydride radio - 6 to 8 swipes are required for this
tion with the 15 contained in the oligomeric hydantoin ° C. The pre-adduct containing, corresponding to the speed at which the wire is passed through the furnace according to the invention, which is then subsequently drawn, is 6 m / min. This speed can be increased to 10 m / min in the usual way as a polycarboxylic acid or polyol without the polyfunctional amines, alcohols or the properties of the enamelled wire being converted from amino alcohols into plastics. With a 6-fold application of lacquer, one can be obtained which, in addition to the hydantoin and imide groups, has an increase in diameter d ₂ (diameter of the lacquered wire and also contains ester or amide groups.) Minus i /, (diameter of the bare wire)

The method according to the invention is achieved in all 25 copper wire) of 64 πιμ, that is, the varnish in the solvent carried out, namely film thickness is 32 πιμ. The lacquer wire that is held in this way at temperatures between 100 and 300 ° C. It is also possible to achieve excellent resistance to both process steps, namely a friction resistance and a particularly good degree of hydantoin ring closure and the subsequent holding in the event of a heat shock load. To combine desimide formation in one reaction step, it has a high abrasion resistance, in that after addition of the isocyanate to the more good dielectric strength and high paint film hardness, the mixture only has a glycine ester after addition.
would give the anhydride component is heated. When testing the resistance to abrasion according to the

By adding catalysts, the NEMA method can be z. B. between 100 and

Reactions accelerated or the reaction temperature achieved 35 150 double strokes, according to the paint film

ralures are degraded. thickness fluctuated between 550

Such catalysts are organic compounds and 600 g.

gen of titanium, lead, copper, iron or earth. The wire is around a thorn of its own

alkalis, for example monomeric or polymeric diameter, so around 0.7 mm, wrapped and so

Titanium butylate, lead naphthenate or octoate, zinc 40 wire helix obtained in a heating cabinet

naphthenate or octoate, placed Kupferhemiporphyrazin, which is preheated to 26O ⁰ C, so can be

Iron acetonylacetone, calcium naphthenate or di- no cracks or breaks in the after 60 minutes

butyltin dilaurate. Amine and lacquer films can also be found (heat shock according to DIN 46453).

Ammonium compounds, especially quaternary When determining the softening temperature

Salts, such as tetramethylammonium fs according to DiN 46453, are added to the coated wire by a

acetate, tetramethylammonium terephthalate, choline-loaded steel pin crossing at an angle of 90 °

octoate, usable. which the weight of 1 kg rests. Between that

From these catalysts 0.1 to 3 ⁰ zo, be steel pin and the copper is a voltage of

drew on the fixed portion, used, higher additions 150 V. This device is in a

While not harmful, ^r abe provide no heating cabinet 50, the temperature by 50 ° C / hour

noticeable advantages more. is increased. In the temperature range in which

The polyhydantoinimides obtained in this way are suitable, the film is softened due to its thermoplasticity, especially for stoving enamels, in particular wire- the steel pin pushes through the enamel film, enamels (electrical insulating enamels). As a result of the direct contact with the Siahl pin and stanchions with regard to the process technology, as well as copper wire, an acoustic signal is triggered with regard to the properties of the coated electrode, which indicates the end point of the test. Particularly diverse with all fresh leaders. Baked coating machines must solution, the paint within the above operating range the different types of orders (400 ⁰ C, 6 to 10 m / min.) To be adjusted. The wire passes in the wire, the furnace could usually pass a lacquer bath up to its final temperature, behind which the over-60 of 330 ° C are then heated without the lacquer-shedding lacquer being pressed through by a special wiper film from the steel pin,
system is stripped. The breakdown voltage, measured on twisted felts through which the wire passes wire samples, (DIN 46453), is between 8, is made up of two. For this procedure, one and 9 kV.

The hardness of the paint film (DIN 46453) is 5 H. This value is required by selecting suitable solutions 30 minutes in preferably from 20 to 30% is achieved. Here, ethanol at 50 ^c C is exposed.

Furthermore, the coated wire does not show any hairline cracks when it is bent under water. To test one bends the wire in a 0.5 ° / uigen saline solution around a mandrel 10 mm in diameter and lays it Apply a direct voltage of 100 V to the water bath and the copper conductor. If there is hairline cracking a current flow would occur and an intermediate control lamp would light up.

The paint solutions used generally contain suitable solvents or mixtures, generally those as already used in the preparation of these imide-modified polyhydantoins became. A certain amount of nonsolvents can also be used. As a solvent you can, for example, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, use aliphatic hydrocarbons, esters and ketones. In particular, are suitable N-alkylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, Dimethylformamide, diethylacetamide, phenol and cresol or mixtures thereof.

The solids content of the solutions can fluctuate within wide limits and is also based on them the type of binder and its dissolving behavior as well as the intended application. As a guide one can probably use solutions with a solids content of 10 to 60 "/« think. For example, in the case of lacquers for lacquering wires on the normally used lacquering machines depending on the type of application and wire thickness, a solid content of about 10 to is used 45 "ι,. Impregnating varnish before, coils Ivsitzen in contrast, as a rule, a solids content of about 35 to 50 "0.

The hardening reaction can be accelerated by adding suitable catalysts, i. H., the reaction time is shortened or the stoving temperature is lowered at the same time. This is This is important for complete curing on particularly high-speed wire enamelling machines. Such catalysts are e.g. B. listed above.

Of these catalysts, 0.5 to 3.0 ° (i, based on the solid content of the paint, used. Higher additions are possible, but no longer bring any obvious advantages.

In addition to using the obtained according to the invention Imide-modified polyhydantoin plastics in the stoving lacquer sector can use these types in find a wider form than temperature-resistant plastics use. Solutions of the imide-modified Polyhydantoins, e.g. B. in cresol or Halogcnaliphaten, depending on the composition means a casting device in a predetermined thickness on a heat-resistant base, the /.B. the end Glass, metal and the like can consist and from which the finished film can be easily lifted off, applied will. By heating to temperatures of e.g. B. 50 to 250 C, the solvent is evaporated and the finished film, which has good mechanical properties at melting points above 300 C, deducted from the pad. In an analogous manner, by means of appropriate spinning devices Fibers made from imide-modified polyhydantoins. especially when using bifunctional Components, d. H. linear plastics. By applying imide-modified Polyhydantoins on fiberglass, silk or asbestos fabric can be pressed into Corresponding laminates with excellent temperature behavior are produced in a manner known per se will. It is also possible, if appropriate, by pressing in the last stage of production under pressure to obtain solid plastics, which can optionally be expanded in foam form with low density can be obtained.

The following examples illustrate further details of the process according to the invention.

example 1

a) 398 parts by weight of N, N'-bis (carbomethoxydimethylmethyl) -4,4'-diamino-diphenylmethane in 400 parts by weight of techn. Dissolved cresol and, after adding 0.2 parts by weight of endoethylene piperazine, added 265 parts by weight of 4,4'-diisocyanatodiphenylmethane, dissolved in 260 parts by weight of xylene. The mixture is allowed to stand overnight and then heated under simultaneous removal of cresol 6 hours at 200 C, wherein it contains 806 parts by weight of 76% strength material having an isocyanate excess of 6 ¹ Vo.

b) 80.6 parts by weight of the 76 "/ oigcn polyhydantoin oligomers thus obtained are added in 200 parts by weight Dissolved cresol and added 1.31 parts by weight of pyromellitic dianhydride at 120.degree. One heats up 6 hours at 200 C and receives 281 parts by weight of a solution that, after diluting with the same Amounts of cresol have a viscosity of 1175 cP.,. having.

A wire produced with this lacquer solution besi'i / i with good elastic properties and with a high heat resistance and abrasion resistance Softening temperature of over 330 C. Stoving the precursor obtained according to a) gives poor elastic properties.

Example 2

a) 398 parts by weight of N, N'-bis (carbomethoxydimethylmethyl) -4.4'-diamino-diphenylmethane are dissolved in 400 parts by weight of cresol and a solution of 300 parts by weight of 4,4'-diisocyanato-diphenylmcthan at 30 C, dissolved in ISO parts by weight of toluene, added. Heated after standing overnight one (5 hours at 200 C and then, after cooling to about 140 C, still carries 77 weights Trimellitic anhydride. The mixture is heated for a further 4 hours at 200 ° C., with the escape being preceded Carbon dioxide can be detected and obtained 1062 parts by weight of reaction product.

Example 3

a) In the manner described in Example 1 a) who which initially consisted of 398 parts by weight of N.N'-bis (car bomethoxx. dimethylmethyl) - 4,4 '- diamino - diphenyl methane in 400 parts by weight of cresol and 325 parts by weight of 4.4'-diisocyanatodiphenylmethane 105 Parts by weight of a 64.3% oligohydantoin Voi stage produced which has an isocyanate excess of 30 "11.

b) 105.1 parts by weight of this precursor are then converted into 110 parts by weight of cresol with 6.54 weight ' divide pyromellitic anhydride at 200 C into an imide-modified polyhydantoin solution (217 weight parts) transferred, which is used analogously to Example 1 b) as Elcktrc insulating material and after dilution with equal amounts of cresol a viscosity of 1115 cP.,. having.

509 616 / J

c) Analogously to 3 a) + 3 b), using a 2 () ″ / o igen isocyanate excess and the corresponding Amount of pyromellitic dianhydride worked, and you get 212.5 parts by weight of a corresponding solution with a viscosity of 1921 cP. “after dilution with equal parts Cresol. "

d) Analog 3 a) + 3 b) is carried out using a 10% isocyanate excess and the corresponding Amount of pyromellitic dianhydride worked, and you get 212.5 parts by weight of a corresponding solution with a viscosity of 2727 cP. "after dilution with equal parts Cresol.

Example 4

From 159.2 parts by weight of N, N'-bis (carbomethoxydimethylmethyl) -4,4 '- diamino - diphenylmethane, <j00 parts by weight of cresol and 0.2 parts by weight of endoethylcnpiperazine, 130 parts by weight of 4,4'-di- ■ isocyanato-diphenylmethane , dissolved in 100 parts by weight of xylene, a pre-adduct is first prepared by heating at 200 ° C. for 2 hours and then 49.3 parts by weight of ethylene glycol bis trimellitate is added to this. After 6 hours heating • 900 parts by weight of a polyhydantoin imidrnodifizierten the same after dilution with cresol ■ quantities obtained at 20 () ⁿ C (with the evolution of carbon dioxide) has a viscosity of 460 cP.,. • and can be baked in the usual way to form a wire enamel ■ with a softening temperature above 330 C, high abrasion and high heat shock.

i Example 5

159.2 parts by weight of N.N'-bis (carbomethoxydimethylmethyl) -4.4'-diamino-diphynylmcthan. 200 parts by weight of phenol, 0.2 parts by weight of Endoäthylcnpiperazin are at 35 C with 90 parts by weight 1,3-Diisocyanatobenzene (140 ",« ig), dissolved in 200 parts by weight Phenol, added and initially heated to 190 C for 2 hours. Then 51.6 parts by weight are added Benzophenone-3,3 ', 4,4'-tetracarboxylic acid dianhydride and heated to 190 for a further 6 hours up to 200 ° C. You get 866 parts by weight of an approximately 34 "(oily lacquer solution, which after dilution with equal amounts of cresol has a viscosity of 546 cP ... and analogously to Example 1 b) to an insulating material with corresponding properties or on a hot roller to form a film with a high Temperature resistance and softening temperature can be processed.

Example 6

In an example analogous to 5, instead of the 159.2 parts by weight of N-N'-bis (carbomethoxydimethylmethyl) - 4.4 '- diamino-diphenylmethane used there, 122.8 parts by weight of N.N'-bis (carboxymethyl-dimethylmethyl) -1,3-diaminobenzene used and 882 parts by weight of a lacquer solution with cP _{; s} --- 221, obtained after dilution with equal amounts of phenol and the same application properties.

Example 7

80 parts by weight of N.N'-bis- (carbomethoxydimethyl-4,4'-diaminodiphenyl ether are dissolved in 300 parts by weight of cresol and 65.6 parts by weight of 4,4'-diisocyanatodiphenyl ether, dissolved in 150 parts by weight of cresol, after adding 0.1 g of endoethylene piperazine a Oligohydantoin converted, S which is condensed by the addition of 13.1 Gewichtsteüen pyromellitic dianhydride at 200 ⁰ C for 6 hours. this gives 453 parts by weight of an imide-modified and linked via Diphenylätherreste polyhydantoin resin that precipitated by were to admit of acetone and after solution in methylene chloride or Phenol can be cast into a temperature-resistant film.

Example 8

159.2 parts by weight of N, N'-bis (carbomethoxydimethylmethyl) -4,4'-diaminodiphenyl ether, 200 parts by weight of phenol and 2 parts by weight of N.N'-dimethylpiperazine are mixed with 101 parts by weight of hexamethylene diisocyanate at 35 "C and the next day at 200 ° C . heated is then added 43.6 parts by weight of pyromellitic dianhydride added and heated for a further 6 hours at 200 C. ^u are obtained 458 parts by weight of about 65 ° / o solution with equal parts of cresol has a viscosity of 4335 CP ₂ after diluting - and having can be processed into a film in an analogous manner.

Example 9

398 parts by weight of N, N'-bis (carbomethoxydimethylinethyl) -4,4'-diamino-diphynylmethane be with

0.7 parts by weight of triethylenediamine dissolved in 1592 parts by weight of cresol, then the Solution of 375 parts by weight of 4,4'-diisocyanatodiphenylmethane added dropwise in 750 parts by weight of xylene. The mixture is then stirred for 10 hours at room temperature

temperature, the temperature increases slowly to 190 ° C. and, after cooling, enters 109 g of pyromeluthic anhydride. The reaction mixture is now ^{heated to 19O ':} C until a clear, viscous solution has formed. The lacquer solution is brushed onto a glass plate and baked first at 210 ° C. and then at 290 ° C. to form an elastic lacquer film.

Example 10

398 parts by weight of N, N'-bis (carbomethoxydimethyl) -4,4'-diamino-diphenylmethane, dissolved ir 1592 parts by weight of cresol are added to the solution

of 240 g of phenylene (1.3) diisocyanate and 0.7 parts by weight of triethylenediamine in 480 parts by weight Xylene added dropwise at max. 30 C. It is now allowed to stand for about 12 hours, the xylene is distilled off and sluggish after cooling, 109 parts by weight of pyromellite

acid dianhydride. Then the mixture slowly heated to 190 to 200 C and 6 hours he kept this temperature. A viscous brown solution is obtained, which is painted on a metal sheet is baked into a clear lacquer film.

Unexpected technical advantages of the fiction, contemporary method over the method dei BE-PS 678 282 results from the following comparative tests:

a) Try after the
Belgian patent 678 282

398 g of bis [methoxycarboxylpropylaminophenyl] methane and 300 g of 4,4'-diisocyanatodiphenylmethane, dissolved in 180 g of toluene, are introduced into 400 g of cresol. The temperature is kept ^{at 30 ° C. by cooling.} The mixture is then left to stand at room temperature for about 12 hours and then heated to 200 ° C. for 6 hours, the toluene distilling off. 330 g of this reaction product are stirred with 110 g of polyester of phthalic acid, ethylene glycol and trimethylolpropane having an OH content of 12 ¹ Vo and 627 g of cresol. This lacquer solution is applied to a copper wire and baked first at 200 and then at 300 ° C. The softening temperature of the paint film, measured according to D! N 46453, is 182 ° C.

b) Experiment according to the invention

398 g of bis [methoxycarboxylpropylaminophenyl] methane are suspended in 400 g of cresol and then

while cooling at about 30 ° C. with a solution of 300 g of 4,4'-diisocyanatodiphenylmethane in 180 g Toluene added. The mixture is left to stand overnight and then heated to 200 ° C. for 6 hours. During this, toluene and split off methanol distill off. Then 19.2 g of trimellitic anhydride entered and stirred at 200 ° C for a further 6 hours. A clear solution of the is obtained Polyhydantoinimides diluted with 1124 g of cresol

ίο is applied to a copper wire. After baking is obtained first at 200 ° C and then at 230 ⁰ C a paint film whose softening temperature, measured according to DIN 46453, is above 330 ° C.

The comparison tests clearly show the unexpectedly superior properties of those according to the invention obtained polyhydantoinimides. Although the polyhydantoin precursor is used in both processes modified by predominantly aromatic nuclei

ao, only the polyhydantoinimides can be used as high-temperature-resistant paints (see the He softening temperature).

Claims (1)

Claim: Process for the preparation of polyhydantoins containing imide residues by reacting a) polyvalent glycine ester derivatives of the formulas HR ₁ - N — C — C R ₂ A modification of polyhydantoins containing isocyanate groups is also mentioned in the patents mentioned described by condensation with polyesters. A processing of these products too Lacken shows that the excellent temperature resistance of the polyhydantoins through this modification is greatly reduced. The subject of the invention is a Ve · .: h ^ en zur Production of poly containing imide residues o hydantoinen by implementing