DE1745437A1 - Imide-amide copolymers and process for their preparation - Google Patents

Description

Societe RHODIACETA, Paris (France) Imide On id-Kopolymerisa te and methods for their preparation

The invention relates to imide-amide copolymers and a Process for their production

So far, two types of polymers are known which contain either imide groups or amide-imide groups.

As already known, the first-mentioned polymers, namely the polyimides, especially the aromatic, excellent heat resistance and good electrical and dielectric properties, so they because of their mechanical properties are interesting and in the form of foils or thin layers as protective and insulating materials, especially for the insulation of electrical conductors, can be used. However, these resins are infusible and insoluble, and only the prepolymer is soluble. As a result, during the manufacture of the molded body,

1 0 9 8 3 7/1 B U 8

for example the foils, based on the solution of the Prepolymers still require a chemical reaction, which complicates the technical applicability of these resins. On the other hand, the films obtained are in certain Felling fairly un bendable and quite susceptible to repeated bending.

The second-named polymers, namely the polyamide imides, are, if they have a higher molecular weight, soluble in certain polar organic solvents, what the production of foils or protective layers from these resins facilitates · These foils and protective layers au3 Polyamide-imides are generally more flexible than the films or protective layers made of polyimides Heat resistance, especially their resistance to oxidation at high temperatures, generally weaker than that of the polyimides.

The copolymer of polyimides and polyamide-imides according to the invention is in the form of macromolecules with high Molecular weight soluble, which is why films and protective layers can easily be produced that combine the increased heat resistance of polyimides with the flexibility of polyamide-imides.

According to the invention, the copolymer is characterized in that that it contains organic radicals R, dia through each other

1098 37 / Ib 48 ^; - '> ί e ^) r

17A5A37

^v residues of the following general formula

ti

C °

^ R ₁ -C-NH-

ti

and the general formula

0 O

tf Il

ti ti

O O

are connected, in which R * and R _{2 is} a trivalent organic Κβί'-t with at least three carbon atoms or a tetravalent organic radical with at least two carbon atoms, the radicals R, R., and R _{2 at} least «ine of the following Have groups: aliphatic, aromatic and alicyclic radicals, heterocyclic radicals with at least one nitrogen .. oxygen or sulfur atom, whereby these groups can be straight or branched, and that rs a macromolecule limited by at least one of the following groups:

Il

C - NH - C - VL ^ J

ti

109837/1548

O
ff < O
ti and ^c \ ' ⁰ N, ti ti O O

dd

⁰ C

HO-C-Rj

It

The copolymer after the Swindling can be linear or crosslinked · In the former case, the radicals mentioned are R divalent and contain at least two carbon atoms. In the second case, only some of the mentioned radicals are formed from divalent radicals, while the other part is formed from n-valent radicals with at least η carbon atoms consists.

The process for the preparation of the copolymers according to the Invention is characterized in that a product in solution, which in the presence of an inert, polar organic solvent by reacting at least one carbonyl compound which is capable of simultaneously a To form amide and an inner ImId and on the one hand a carboxyl group and on the other hand a pair of carbonyl groups contains, each of which on the one hand with a different carbon atom of the same trivalent radical and on the other hand linked to an oxygen atom, the two carbonyl groups being connected by a maximum of three carbon atoms are separated and wherein the carboxyl group is separated from each of the carbonyl groups by at least two carbon atoms is separated, with at least one Dilsocyanat or a mixture of at least one Polylsocyanat and at least

109837/1548

a diisocyanate is obtained, the amounts of diiso « cyanate, polyisocyanate and carbonyl compound are such that each NCO group has half a mole of carbonyl compound is equivalent to! adding a product in solution which, in the presence of at least one inert, polar organic solvent, reacts with at least one tetracarbonyl compound which is capable of forming an internal diimide and the two pairs contain carbonyl groups, each of the Groups on the one hand with a carbon atom of the same tetravalent radical and on the other hand with an oxygen atom is connected, the carbonyl groups belonging to the same pair being separated by a maximum of three carbon atoms are, with at least one diisocyanate or a mixture of at least one polyisocyanate and at least one Diisocyanate and / or a mixture of these starting materials is obtained, the amounts of diisocyanate, polyisocyanate and on carbonyl compound are such that each NCO group corresponds to half a mole of carbonyl compound, and thereby, that this mixture of substances in solution to form a copolymer at a temperature below 100 ° C lets react.

This means that the process according to the invention consists in using a linear or crosslinked polyamide-imide in solution with a linear or crosslinked polyimide converts to I <ö3üng »

■ »t> ··! 0 9 H 'JV / 1 5 A Ö

The extraction of linear or cross-linked polyamide «sorry in solution, as used in the method according to the invention, is detailed in the patent application . ... ... (patent application S lOli 751 IVd / 39c).

The extraction of linear or networked pdynes in

The solution is in the design pamphlet (patent application S 104 497 IVd / 39c).

As Carbony! Compounds that are in the Luge, at the same time Forming an amide and an internal imide uses aan Tricarboxylic acid monoahhydrides, tricarboxylic acids or a Genetically made from lionoanhydride and corresponding acid, each of which has the following general form:

O O

Il <Il

HO-C- R, ^, 0 or HO-C- B

¹ y ^

C-OH

• I Il

0 0

in which R, has the meaning given above.

The carbonyl compounds used are preferably those of the above formula in which R _{1 contains} several of the above-mentioned groups which are linked either directly or intermediately by at least one of the following radicals: -SO ^ -, -0-, -CO-,

0 Y -P-, -C-, -NY-CO-X-CO-NY-, -CO-HY-X-NY-CO-, -CO-O-K-O-CO ··,

^{Y r} ΊΠ98Π7 / 15Α8

-O-CO-X-CO-O- and -CO-NY-NY-CO-, where X is a divalent alkylene radical, dioxyalkylene radical, cycloanilidene or arylene radical, Y is an alkyl radical, an aryl or cyclanyl radical or hydrogen and Y * is an alkyl, aryl or cyclanyl radical.

The tricarboxylic acid monoanhydrides are preferably the the following is used:

Trimellitic acid monoanhydride a

Naphthalene-2,3, C-tricarboxylic acid-2,3-aonoanhydride Dipheny1-3,4,4 * -tricarboxylic acid-3,4-nonoanhydride Naphthalene-1,8,4-tricarboxylic acid-1,8-monoanhydride NaphthaXen-1, 2, 5-tricarboxylic acid-l, 2-aonoanhydride Diphenylsulfon-3 _f 4,3 * -tricarboxylic acid-3,4-monoanhydride Perylene-3,4,9-tricarboxylic acid-3,4-nonoanhydride Diphenylether-3,4,4 * tricarboxylic acid 3,4-monoanhydride tricarballylic acid monoanhydride Cyclopentadieny1-1,2,4-tricarboxylic acid 1,2-monoanhydride

Benzoi} henon ~ 3,4,4 * -tricarboxylic acid-3,4-monoanhydride ™

2- (i> iearboxy ~ 3 ', 4 * -phenyl) -5 (carboxy-3 ^f -phenyl) -1, 3,4-oxadiazole-3', 4'-monoanhydride

2 {]) icarboxy-3 ', 4 * «phenyl) -5-carboxybenzimidazole-3 *, 4 * - Bono anhydride

2 (dicarboxy-3 *, 4 * -phenyl) -5-carboxybenzoxazole-3 *, 4 * -mono anhydride

2 (dicarboxy-3 *, 4-phenyl) -5-earboxybenzothiazol-3 ^f , 4 * -monoanhydr jd

109837/1548

2 (dicarboxy-3, 4'-diphenylather) -5 (carboxy-4-diphenylather) -

1,3,4-oxadiazole-3 *, 4 ^f -monoanhydride 4 * (dicarboxy-3,4-phenyl) -carboxyaethannonoanhydride 4 '(dicarboxy-3,4-phenyl) -carboxypropanaonoanhydride

The tricarboxylic acids used are expediently those corresponding to the monoanhydrides mentioned above. If you use a mixture of monoanhydride and 8 acid, the sturdy used is that of the monoanhydride.

As diisocyanates, the "to the production of the polyamide Iaido used for the production of the invention with the mentioned carbonyl" Reacts compounds, uses "at least one diisocyanate of the following general formula

O-C- H-R-N-C- O,

in which R is a divalent radical of at least white carbon and has the meaning given above. The diisocyanates used are preferably those in which the radical R contains several of the groups mentioned, the latter being linked directly or through at least one of the radicals are as indicated for the compounds of R ₁ , or by at least one of the following radicals: -MT-SO ₂ -X-SO ₂ -MT- and -SOj-HT-X-MT-SOj-, whereby

X and T have the meaning given in the foreground »

'- ■ · -1 09837/1548

So all diisocyanates of this general formula are used preferably the following isocyanates:

Dipheny1-2,2-propane-4,4 * -diisocyariat

I.

Dipheny ^ methane-4,4 * -diisocyanate Dipheny1-4,4 * -diisocyanate Diphenyl sulfide-4,4 * -diisocyanate Diphenyl ether, 4,4 * -diisocyanate Dipheny1-1,1-cyclohexane-4,4 * -diisocyanate Bie («- pli« nyl-ieocy »nÄt) -BiGthyl-phoephinoxid Naphthalene-1,5-diisocyanate

m-phenylene diisocyanate

Tolylene diisocyanate Dipheny 1-3,3 * -dimethy 1-4,4 * -diisocyanate Dipheny1-3 _t 3 -dimethoxy-4,4 * -diisocyanate

m-xylylene diisocyanate

Dicyclohexyl ethane-4,4'-diisocyanate hexamethylene diisocyanate etc. Dodecamethylene diisocyanate Dodecane-2,11-diisocyanate

p-phenylene-bisCp-phenylene-1,3,4-oxadiazole-isocyanate)

I ₁ 3,4-oxadiazole bis (p-phenylene isocyanate)

1,3,4-0xadiazole-bis (m-phenylene-isocyanate) 4-phenyl-1,2,4-triazole-bis (n-phenylene-isocyanate) (2-phenylene) benzimidazoles, 4 * -diisocyanate (2-phenylene) b € nzox * zol-5,4'-diisocyanate

(2-phenylene) benzothiazole-6,4'-diisocyanate

109837/1548

- 10 -

Bis-2,5 (2-phenylene-isocyanato-benzlmldazol-eyl) -l, 3,4-

oxadlazole

Bis (p «phenylene-> i8ocyanato-2-bensijiidasol-eyl) Bis (p-phenylan-isooyanato-2-benzoxaaol-e-y1)

The polyisocyanates which are used in a mixture with the or the diisocyanates have the general formula

R <-N - C - O) _n ,

in the .η an integer of at least 3 and R, the one n-valent radical with at least η carbon atoms, otherwise corresponds to the definition given above.

In the event that the remainder R * contains several groups, are these are preferably connected to one another either directly or intermediately by at least one of the following radicals:

(It

, 000 ▼ SO »-, -0-, -CO-, -C-H, -O-Si-0-, O-P-O-, S-P-O- and 0-P-

0 0 0

t 1 t

The polylaocyanates used according to the invention are preferably trisocyanates, in particular the following:

Triphenylmethane-4,4 *, 4 "-triisocyanate Diphenyl ether 2,4,4'-tri-oxyanate Triphenyl phosphate 4,4 ·, 4 "-triisooyanate

- 11 -

109837/1548

Triplienyl thiophosphate 4,4 · ^ "- triisocyanate Triphenylphosphine oxide ~ 4.4 ^t , 4 ^tl -triiaocyanate

1-methylbenzene-2,4-triisocyanate 1,3,5-Tr June thy lbenzol-2,4,6-tr iisocyana t

Naphthalene-1,3,7-triisocyanate Dipheny1-2,4,4'-triisocyanate

3-methyldiphenylu »ethane-2,4,4 * -triisocyanate

Other polyisocyanates can also be used, as »B. 4,4 * -Dimethyldiphenylaethane-2,2 *, S, 5'-tetraisocyanate, Tetraphenylsilicate-etraisocyanate, a polyphenylene-polymethylene-polyisocyanate and a polyoxymethylene-polyisocyanate.

As tetracarbonyl compounds that are able to use a

to form inner diimide is used tetracarboxylic acid dianhydrides, tetracarboxylic acids or mixtures of dianhydride and the corresponding acid, each having the following ¹

have general formula:. . Λ

it ι · _< η η

HO - C C-OH baw. R ₂

HO - (T ^ C-OH

η ι «

in which R _{2 has} the meaning given above. The carbonyl compounds used are preferably those of the above formulas in which R _{2 contains} several of the above-mentioned groups, either directly or through at least

109837/154 8 '

- 12 -

one of the same residues are connected as they are mentioned for the compounds of H ₁ .

The following are used as dianhydrides; Py r ome hi tic acid edianbydr id Naphthalene-2.3 _{t over} , 7-tetracarboxylic acid dianhydride Dipbeny1-3.3 ·, 4.4 · tetracarboxylic acid dianhydride Naphthalene-1,4,5,8-tetracarboxylic acid dianhydride Naphthalene-1,2,5, b-tetracarboxylic acid dianhydride Bls (dicarboxy-3,4-phenyl) sulfone dianhydride Perylene-3,4,9,10-tetracarboxylic acid dianhydride Bis (dicarboxy-3 _t 4-phenyl) ether dianhydride Ethylene tetracarboxylic dianhydride Cyclopentadienyl tetracarboxylic dianhydride Benzophenol-3,4 _f 3 ', 4 · -tetracarboxylic acid dianhydride

2,5-bis (dicarboxy-3 · , 4 · -phenyl) -1,3,4-oxadiazole dianhydride

Bis (dicarboxy-3 *, 4 * -pheny1-1,3,4-oxadiazole) -p-phenyl dianhydride

2- (Dicarboxy-3 *, 4 * -phenyl) -5, ti-dlcarboxybenzimidazole dianhydride 2- (Dicarboxy-3 *, 4 * -pheny1) -5,6-dicarboxybenzoxazole dianhydride 2- (Dicarboxy-3 ·, 5 · -phenyl) -5,6-dicarboxybenzothiazole dianhydride 2,5-bis (dicarboxy-3 * _> 5 ^> -diphenylether) 1,3,4-oxadiazole dihydric 4

Bis (dicarboxy-3,4-phenyl) methane dianhydride Bis (dicarboxy-3 _t 4-phenyl) propane dianhydride

The tetracarboxylic acids used are those corresponding to the dianhydrides given above.

109837/1548 -13-

The polyisocyanates that have been described with the obsn Carbonyl compounds are the same as those which one for the production of the polyamide-imides in solution aur Brings reaction, which are already mentioned above.

If diisocyanates are used as compounds containing isocyanate groups for the production of polyamide-imides and polyimides in solution, as are used according to the invention, then the molecular structure of the copolymer is linear. If, on the other hand, polyisocyanates which differ from the diisocyanates are used in the preparation of one of the substances mentioned in solution, more or less crosslinked copolymers are obtained in accordance with the proportion of polyisocyanate.

The crosslinking generally increases the thermal and chemical resistance of the resins obtained, but decreases it however, the flexibility of the films made from these resins tends to decrease.

According to the invention, use is made of inert polar organic training agents, preferably NJi-dimethyl acetniaid, Ν, Ν-dimethyl- £ ocmnuiiu , N-methyl-II-pyroliflone and dimethylai oxide »Man Li'Ui. eltunso jJi4 fiomiöcli mm these IiOsüiigsmittel or e sa fiuiiiiictü UU3 dt <? r> on and nnd η inert solu ~ <} uiiK'smittti in, x </ i ". ''fiii'.iK'l.'iViei; ■ ti X / Xol, <. ».» * I '»n ii κ! Ui- odor ' Vi i;> (.nyienijiy i; · .'ti: ·: I ·> ♦ / ■! -J i: <WfUJtU η.

.109837 / 1548

BATH

The reaction temperature should exceed 100 ° C ηlebt, if one wishes to obtain a copolymer in solution, because this precipitates when the heating temperature is higher lies.

From the reaction of the polyamide-imides and the polyimides in Solution, a copolymer is obtained in solution, the molecular weight of which is a function of the molecular weights of the Polyamide-imides and the polyimides reacted with them.

When this solution of the Copolymer to a suitable temperature, optionally at a pressure below atmospheric pressure, a film is obtained which at the same time has good mechanical properties, such as flexibility, tensile strength and excellent heat resistance.

One can also add a nonsolvent too the solution to precipitate the copolymer in solution in order to obtain a copolymer powder that is under Pressure can deform to form molded bodies after heating to a suitable temperature and for a sufficient time obtain.

Example 1 Dissolve and stir ;; at 80 ° C 45 g j »<Lphenylatotuftf * -4,4'-

(iii : .v -;:; jr't and 3-lr »/ V. ino i 1. λ Lfiftureraono & nhydride in 3tiO ecm

109837/1548 BAD ORK ₁₁ NAI. - ₁₅ -

N ~ 2 ~ MethyX-pyrro3idon "ftaeh dor resolution is gradually increased, the temperature aährend seven hours 200 ° C to give N & eh erhiUt cooling to normal temperature, a solution with a viscosity at 25 ° C 250 cP.

In addition, 13 g of diphenyl-1,1-cyclohexane-4,4 * -diisocyanate are dissolved and stirred at 40.degree and 8.930 g of pyromellitic dianhydride in 135 ecm Ν, Ν-Dimethylacetaraid and pour the solution obtained in a cylinder 500 cm long and 5 cm diameter and stirred with a "Vihromixer", wherein nitrogen is passed through the solution for five hours (in an amount of 60 l / h) and the Temperature of 40 ° C is maintained. A slightly viscous solution is obtained in this way.

45 g of the first solution are then mixed with the same amount by weight of the second solution and the mixture is evaporated the mixture of these solutions by heating them to 70 ° C under a pressure of 15 mm Hg until the viscosity this mixture reaches 120 per cent without, however, the mixture at the same time assumes a gel-like consistency. A layer of this viscous mixed solution is then poured onto one Glass plate, heating this plate to maintain the mixed solution temperature at 70 ° C. Man the temperature is then gradually increased to 130 ° C. at a pressure of 100 ram Hg over a period of four hours, then the temperature is increased

109837/1548 * " ^1Ö ~

the pressure to atmospheric pressure, and then you increase the Temperature for three hours at 250 ° C, after which this the latter temperature maintained for more than four hours · Then it is allowed to cool to normal temperature and the film obtained is removed by immersing the plate in water.

30 g of the first solution, as described in the previous example, are mixed with 60 g of the second solution of this example and produces a film in the manner described in this example.

Beis piel 3

Are mixed and the mixture is stirred for several minutes at ambient temperature, 12 g of B described in _e 1 ispiel first solution with 120 g of the second solution of this example and is then added to this Lösungsgeralsch a solution of 1 g Triphenylthlophosphat-4,4 *, 4 "- triisocyanate and 0.7 g of pyromellitic dianhydride in 12 ecm, Ν-Dlmethylacetamld The whole thing is stirred for a few minutes at ambient temperature and then quietly made a film from this mixed solution using the method described in the preceding examples.

Example 4

Dissolve and stir at 80 ° C 6 g Dlphenylftther ~ 4.4 * "diiao cyanate and 4.59 g Trlmellltsäuremonoanhydrid in GO ecm N-methyl-2-pyrrolidone, and then increased after resolution within

109 837/1548

- 17 -

half "on siοbon hours gradually raise the temperature 300 ° <J to obtain a viscous solution.

In addition, 7 g of diphenyl ether 4,4'-diisocyanate and 6.055 g of pyromellitic dianhydride in 70 cc * N, N ~ dimethyl ~ acutawAd and pour this solution into a container old £ laugh floor with 600 cm "surface, which during two

Hours at 40 ° C is kept.

You nibble 20 g of the er3ton solution old of the same weight amount of the second and then adjust to the Weiao described in Example 1; Slide.

If you put the film in the atmosphere for 63 hours at 300 ° C

heated, it loses 3.3% of its original weight, what dom weight loss (3.2%) for the same conditions is comparable to that of a polyimide film obtained by

Implementation of UiphenylätUur »4 _l 4 ^l -diieocyanate with Pyromellit- ™

acidic anhydride, erluidut. The resistance to sagging is yours

Foil is good, especially after three days of heat

300 ° 0, while a film from Po I yam id-Imi ti is obtained by implementation of i * lphynyläthor-4,4'-diio4 »cyanate and

TriuoLlitaUuremonoanhydt id bei rliesun B £ ldiiiguu, | un

109837 / 1S48 _βΔηΛΒ

The following table clearly shows the WärnobuHtc'ui.Uj ku i. expressed by the relative Gewioht.jvarluat one Sample in air for different times bol 300 ° C was held.

sample Weight loss in%
after heating in air
at 300 ° C 4.5 ti, J After this
example 3. 4.5 9.0 Diphenyl ether
pyroaellite
Poly imide 3, 7.1 10.4 Diphenyl ether
trlraollit-
Polyaaid imide 5, , 5 , 3 7th

Stability g ,,>'itriodorh> ltns CAt ^ \ under «ine * wiuki / t. from 180 ° to ÜJ constant Krh i I: η

good Good

bad

This FlIa has the values given in the following table »» mechanical properties:

B «l, 3a ° C

At 300 ° C.

Strength Bruciutehiiiing Ct) strength; Hruchdahnun; (JLi » kg / wufi) If ¹¹ ^ ^-111 IL ⁽ ? 2

Ii ?, 1 /, * »Ii ₁ O 1.1

Dutch thormojjrairl · · * t.rt η "Ί.ο Μ« »ti.iUn..rg With HlI ^? -

{tht> di.iuilttiu: u) (Lu liMuiol later «it .. ik» C3lchn.ti> g ")» tf.il t uaa υ Latin 4o ^ 4Bgä «ich do vertuet at 310 ° C firmly,« ei * «Working on U Ulft, wot-t 4% <* ν * Tür ait gluichaJUllgei tieaoewiadtfMit

1 ü 9 8 3 7/1 5 4 8 wlrl.

3.2 ⁽ C / al "

BATH ORIGINAL

Μ - * · »removes 10 g diphenyl ether-4,4 * - while sweeping at 80 ° C

. 1 g · Triphenylraethnn ~ 4 _t 4 ^f, 4 ^tf triisocyanate and 8.17 g Trimellitsäuremonofuihydrid in 100 cc of N-Methylpyrrolidop, then after dissolution the temperature is raised to 100 ° C and this Temperntür maintains three hours wherein eiri? brown and viscous solution is obtained.

15 g of diphenyl ether-4 _f 4- ~ diisocyanate, 1.5 g of tri.phenylethane-4,4 *, 4 "-triisocyanate and 14.3 g of pyro & ellite dianhydride are dissolved in 150 g of NN-dimethylacetamide, while stirring at 40 ° C, and the solution obtained is poured into a flat-bottomed container with a surface area of 1200 cm, which is kept for two hours in an oven at a temperature of 40 ° C. A gel-like colloid is obtained, which is poured into a flask, in which this colloid is heated for one hour at 100 ° C under vigorous guidance, whereby a viscous, brown, non-gelling solution is obtained.

A copolymer film is prepared by mixing 20 g of each of the two solutions and then proceeding as described in Example 1.

This film has the following mechanical properties (measured at 22 ° C):

- 20 -

109837/1 5 A 8

Strength 10.1 kg / mm ² Elongation at break (related

on the original 10.3%

Length)

At 200 ° C the loss in strength is 52%, and the Elongation at break increases to 186%

An initial weight loss at 320 ° is established by thermogravimetric determination under the conditions given in Example 4. C fixed.

Example 6

To the mixture of 70 g of each of the two solutions prepared according to Example 4, namely the solution of polyamideimide and the solution of polyimide, a solution of 16 triphenylmethane-4,4 ', 4 is added with stirring at ambient temperature for ten minutes ^M -triisocyanate and 0.9 g of pyromellitic dianhydride in 11 ecm of N, N-dimethyl acetamidon.

The catfish given in example 1 are then placed on a copolymer film

This film has the following mechanical properties (measured at 22 ° C):

Strength 11.01 kg / mm ^a Elongation at break (related

on the original 13.9%

Length)

- 21 -

109837/1548

At 200 ° C the loss of strength is 45%, and the elongation at break increases, among other things, 67 %,

To the first solution of Example 4, add “under Bübren at 40 ° C add a solution obtained in the following way:

Dissolve 3 g of DiJMienyläther-4,4 ^f -diisocyanate, 2.07 g of pyromellitic dianhydride and 0.54 g of pyroaellitic acid in 45 cc of N-dinetbylacetamide and heat for two to three minutes at 70 ° C in order to obtain a homogeneous solution. This solution is poured into a flat-bottomed container with a surface area of 600 ca, which is kept at 40 ° C for two hours.

A solution of 1.3 g is added to the mixture of these two solutions with stirring at 40 ° C. for 30 minutes Tripbenyl thiophosphate 4,4 *, 4 "-triisoejraaat and 0.845 g Pyromellitic acid planhydride in 20 cc »lf ~ diaethylacetaald.

Then proceed in the manner indicated in Example 1.

The heat resistance of this filate is older than that Example 4 obtained fiInes comparable.

Patent claims :

* "109837/1548

Claims (1)

20 332 Societe RBQDUCBTA ₉ Pariah (France! P. ft Λ..ft ^ρ * * ρ , ^a p . y M l, .c ft .fn.ii % 1. Imide ~ amide copolymer, thereby connected, because it contains organic radicals R, which are interconnected by radicals of the following general formula and the general formula t 0 0 ψ η η η η are connected, in which R. and R _{2 is} a trivalent organic radical with at least three carbon atoms or a tetravalent organic radical with at least a few carbon atoms, the radicals B ₉ B ₁ and - 2-1 09837/1548 have at least one of the following groups: aliphatic ^, aromatic and alicyclic radicals, heterocyclic radicals with at least one nitrogen, oxygen or sulfur atom, it being possible for these groups to be straight or branched, and that there is one by at least one of the following groups limited macromolecule is: O 0 0 it ti ti Op r r - NH - C - R ^ ^ P, - N ^, R ₀ , 0 and it Ii tt Il Il HO-C-Ri ^ N- It 2. Copolymer according to claim 1, characterized in that ä said radicals R are divalent and contain at least two carbon atoms, the copolymer from linear chains is formed. 3. Copolymer according to claim 1, characterized in that dafi at least some of the radicals R mentioned are formed by divalent residues, the other part being composed of n-valent There are residues with at least η carbon atoms, and that the Kopolynsrisat is a three-dimensional macromolecule. 109837/15 U 8 -3- 4 · Copolymer! sat according to claims 1 to 3 *, characterized in that in the event that the radicals R are several groups contain, if R is divalent, these with one another by at least one of the following radicals: -SOg-, -0 », OY -CO-, -P-, -C-, NY-CO-X-CO-NY .., -CO-NY-X-NY-CO-, ι · YY ¹ -CO-OXO-CO-, -O-CO-X-CO-O- and -CO-NY-NY-CO-, -NY-SO ₂ -X-SO ₂ -NY- and -SO ₂ -NY- X-NY-SO ₂ -, where X is a divalent alkyl, dioxyalkyl, cyclanllidene or arylene radical, Y is an alkyl, aryl or cyclanyl radical and Y 'is an alkyl, aryl or cyclanyl radical, and if R n- is valuable by at least one of the following residues t t t 0 0 0 -0- Si-O-, 0 ·} -Ο., Β · Ρ- and 0 - P - «T · I O OQ t · t are connected, 5. Copolymer according to claim 1, characterized in that in the event that the radicals R ₁ and R ₂ contain larger groups, these latter are linked to one another either directly or through at least one of the following radicals: OY -SO ₂ -, -0-, -CO-, J? - _t -C-, -NY-CO-X-CO-NY-, {Y · -CO-NY-X-NY-CO-, -CO-O-X-O-CO-, -O-CO-X-CO-O- and 109837-548 . "CG-NY-NY-CC-, where X is a divalent alitylene, cyelanilidene or arylene radical, Y an alkyl, aryl or cyelanyl radical or hydrogen and Y * © in alkyl«, -aryl «" or cycl «» any! rest is S "Process for the production of Zmidrenid" Kopolynes? Is & teR, characterized in that mats on a product in Läsimg "■ which in the presence of at least one inert, polar" organic solvent by reaction at least "" Carbony! Compound, which is capable to form giei © to3dt% one-amide and imide eim inside! ut & ®lti € f £ D® & tB üarbosylgruppe and on the other hand a pair - contains, each of which on the one hand has a stoffatoo of the same trivalent Eest «a % mü ^: with an oxygen atom bond · « %, *% carbon groups are separated by a maximum of three loltleturtfOf tMtm.® and where the carboxyl group of Carbony groups through at least two carbon atoms OK ·; , is separated _v with at least one Diieocy & nat osf, it is obtained mixture of at least one "polyisocyanate and a Oiisocyanat, the amounts of" q Biisocyanat, polyisocyanate and carbonyl compound! are each NCO group dad corresponds to half a mole Carbony.lverbindung , a product in solution sweats, because "in the presence of at least one" inert, pOÄT "ß, org * nlech" ü, solution "a | itt # l dyjrch ü" setatung by w * Bigst- "o · · 1ιι «ιτ Tetra» snrbonylyerbiRduiig di «indtr Lüg« is, «in i» o «#» 1 * 0837/1848 Sador ^, - · - ^! % - - _ .- ■■ -. ■. ■ - ■■■■■ * ;. to form and contains two pairs of carbonyl groups, where each of the groups on the one hand with a carbon atom of the same tetravalent radical and on the other hand with one Oxygen atom is linked, being the same pair belonging carbony groups are separated by a maximum of three carbon atoms, with at least one diisoeyanate or a mixture of at least one polyisocyanate and at least one diisocyanate and / or a chemical of these Starting materials is obtained, the amounts of diisocyanate, polyisocyanate and carbony compound being such that each NCO group corresponds to half a mole of carbonyl compound, and by having this mixture of substances in solution Formation of a copolymer in solution with one under 100 ° C temperature to react. »^ The method according to claim Θ, characterized in that the called carbonyl compound, which is able to simultaneously form an amide and, in the inner XmId asu, a tricarbon- acid monoanhydride of the following formula 0
η HO - C - if
0 1st. in which B _{1 has} the meaning given in claim %. ■ '■> ■ - ^ * ft' 4f ^r <'' ■, · "·; ■ · * ■ O · " 8. The method according to claim 7, characterized in that in of the above-mentioned carbony compound, the remainder R., several groups which are linked directly or through at least one of the radicals specified in claim 5 « 9 "V _G rverfahren according to claim 7 or 8, characterized in that said monoanhydride is at least one of the following * trimellitic acid monoanhydride, cyelopentadienyl-1,2,4-tricarhonic acid-1,2-raonoanhydride, diphenyl ether-3,4,4 * - triearboxylic acid-3,4-monoanhydride, l, 3- (dicarboxy «3 *» 4 ^f phenyl) -> 2 (carboxy-3 ⁹ ~ phen ^ l) -5 »oxadiazole-'3 ^f , 4 ^f -iaonoanhydride and ipS ^ -N & phthalene-tricarboxylic acid-ljS-monoanhydride. 10. The method according to claim 6, characterized in that the called Carbony! compound, which is able to simultaneously to form an amide and an internal imide, a tricarboxylic acid of the following general formula tt - S _C - OH HO-C- R ^ , ^V C - OH
μ ■ in which R ^ has the meaning given in claim 1. 11. The method according to claim 10, characterized in that the said tricarboxylic acid at least one of the following acids is: trmellitic acid, diphenyl ether-3,4,4 * -trlcarboxylic acid, (Dicarboxy-3 ·, 4 · -phenyl) -2 (carboxy-3'-phenyl) -5-oxadiazole-1,3,4 and cyclopentadienyl-1,2,4-tri-carboxylic acid. 12. Zerfahren according to claim β, characterized "in that the said diisocyanate is one of the general formula O-C-N-R-N-C-O is in which R is a divalent radical with at least two Is carbon atoms and those specified in claim 1 Has meaning 13. The method according to claim 12, characterized in that in the said diisocyanate, the radical R has several groups which are directly or through at least one of the following Residues are connected: -80 «-, -0-, -CO-, OY .p., -C-, -NY-CO-X-CO-MY *, -CO-MY-X-IIY-CO-, -CO-O-X-O-CO-, Y Y -O-CO-X-CO-O- and -CO-NY-MY-CO-, -NY-SO ₂ -X-SO ₂ -NY and -SO ₂ -HY-X-NY-SO ₂ -, where X and Y 'have the meaning given in claim 5 and Y is an alkyl, aryl or cyclanyl radical 14. Method according to claim 12 or 13, characterized in that that said diisocyanate is at least one of the following 109837/1548 " ^e " is: hexamethylene diisocyanate, dodecamethylene diisocyanate, Diphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, tolylene diisocyanate, 1,3,4-oxadiazol-bia (p-phenylene isocyanate), diphenyl-1,1-cyclohexane, 4 * -diisocyanate and iH.phenylpropane-4,4'-diisocyanate 15 «The method according to claim β, characterized in that the said polyisocyanate is one of the general formula R ¹ <-N «C - O) _n is, in which η is an integer of at least 3 and R * «in is an n-valent radical with at least η carbon atoms, which also has the meaning given in claim 1 for the radical R 16. The method according to claim 15, characterized in that in the polyisocyanate mentioned, the radical R * contains several groups which are directly or through at least one of the following the radicals are connected: -SO «, -, -0-, -CO-, -C-H, • t ι 1 » 0 0 0
tt «t -0-8 i-0-, OHP-O-, S-P- and Q-P-. I »t 0 0 0
ft « 17. The method according to claim 16 or 15, characterized in that because "this is called polyocyanate" in triocyanate. 109837/1548 18 · The method of claim 16 or IT ₉ characterized in DAA DAA said Trilaoeyanat is at least one of the following: Trlphenylaethan _4-f 4 * 4 ^*> -triiaoeyanat ₉ triphenyl-4,4 * ⁿ 4 triisocyanate and triphenyl-4 , 4 ^t , 4 ^M - - trliaooyanat. 19. The method of claim 15 or 16, characterized in that said daft Polylsocyanat 4.4 ^l -di »ethyl-diphenyl-methane-2 _t 2 _{'> 5>} 5 * -tetraisocyanat 1st. 20. The method according to claim 15, characterized in that it is rewarded called polyisocyanate is a polyphenylene-polyethylene polyisocyanate 21. The method according to claim 6, characterized in that the daft called tetracarbonyl compound mentioned in the / Age 1st Form an inner dilution, a tetracarboxylic anhydride the general formula OO η η η η 0 0 is in which B ₂ is as defined in claim 1 has - 10 - 109837/1548 22. The method according to claim 21, characterized! _{that the radical R 2} in the carbonyl compound mentioned contains several groups which are linked directly or through at least one of the radicals specified in claim 5. 23. The method according to claim 21 or 22, characterized in that said dianhydride is one of the following: pyromellitic dianhydride, cyclopentadienl-tetracarbon-sfturedianhydride, benzophenone-3,4,3 *, 4 * -tetraoarboxylic dianhydride, bis (dicarboxy-3, 4 ^f -phenyl) -2,5-oxadiazole-l _v 3,4-dianhydride and naphthalene-l ^ de-tetracarboxylic acid lanhydride 24. The method according to claim 6, characterized in that the dafi called tetracarbonyl compound capable of inner diimide is a tetracarboxylic acid of the following general formula 0 O ti η HO-C. C-OH HO-C ^ - OH tf M in which R _{2 has} the meaning given in claim 21 or 22 Has. 25 · The method according to claim 24, characterized in that the said tetracarboxylic acid is one of the following: pyromellic acid, benzophenone-3,4,3 *, 4'-tetracarboxylic acid, 109837/1548 - 11 - Bis (3,4 ^{dicarboxy-1-phenyl)} -2,5-oxadiazol-l, 3 _f 4 and cyclopentadienyl tetracarboxylic acid. 26. The method according to claim 6, characterized in that the inert, polar organic solvent is at least one of the following: N, N ~ Dim @ thylacetamid, Ν, Ν-Dimethylforaaraid, N-methyl-2-pyrrolidone and dimethyl sulfoxide. 27c method iia: ■ Claims 6 to 26, characterized in that one eats the ge *> -.- r-r.r.e Xsiid-Amid-Kopolymerisat solution to a Pour thin Schi. -M on a surface and at least the boiling point of the solvent is heated so that this Temperature for the temperature necessary for evaporation of the solvent Time to keep the temperature up to more than 200 ° C and that this temperature is maintained for the time necessary to obtain a solid film 28. The method according to claim 6 to 26, characterized in that said copolymer is in solution for precipitation of the copolymer in powder form is a nonsolvent added - BAD ORfGiNAL 10 9 8 3 7/1548