DE1795136A1 - Aromatic polymers and processes for making them - Google Patents

Description

The term "refers to aromatic polymers and especially on improved production of aromatic

Polyimides, '

For example, see British patents 393 651, 903 271, 903 272, 935 338, 942 025 and 1 059 929 described, - can aromatic polyimides. I by condensation of aromatic Setracarbonsäurediarhjdriden II (or the corresponding di- or tetraesters) and aromatic diamines III in solution in a very strongly polar aprotic solvent, v / ie!, H-Dinethylformamide or !!, N-Dimethylacetamide, are produced., a polyamic acid IY is formed as a soluble intermediate product · and to the polyamide I

009850/1987

by. Removal of water under a ring nut along the poly-neck rivet can be grounded unmodified.

! I

(II)

Il

KO - C,

(III)

NK -

V- 'C- OK

Il

(IV)

- NH

or isomer

Il

V V

ti

Il

(D

ν;. O

009850 / 1S67

BATH ORIQINAL

In these proteins, E is a tetravalent residue of aromatic character due to the carbonyl groups of each pair in ortho or peri-position to one another, and H ^{1 is} a divalent residue of aromatic character. R and R ¹ can be aryl radicals derived partly from benzene or naphthalene, but preferably at least some of the radicals R or R ¹ along the 2ol; -;: Grenlcetten are the more flexible bridging aromatic coughs, "derived from compounds of the formula

wherein X sB -0 -,.-3-, -SO-, -SO ₂ -, -CO-, -COIIH- or an alkylene- { _{e.g. -CH 2} - or (- (CII ₅ ) ₂ -> Re st can be.

Examples of the dianhydrides are pyronellitic dian hydri.d, dianhyarides, which are derived from fused aromatic syn, v / ie in IIaphthalene-2,3,6,7-tetracarbon-

acid dianhydride, kaphthalene-1,2,5,6-tetracarboxylic acid anhydride, Kaphthalene-l, 4,5,0-tetracarboxylic acid dianhydride and perylene-33, <-, 9,1O-tetracarboxylic acid dianhydride, and dianhydrides in which the anhydril groups on various interconnected Bensol rings s. Sit, as in Biphenj '"l-3,3', 4, A'-tetracarboxylic acid dianhydride, Biphenyl-2,2 '^, S'-tetracarboxylic dianhydride, 2,2-3is- (3,4-diearboxyphenyl) propane dianhydride, bis (3,4-dicarbo: \ 3-phenyl) ether dianhydride, Bis (3,4-dicarboxyphenyl) sulphondir.niiyclrid, Ben:; ophenon-2,2 '■, 5 »3' -tetracarbongäuredianhydrid und 3eri3oplienoii-3,3 ', 4,4'-tetracarboxylic acid di anhydride. The .general

0 & 9850/1967

BATH ORIGINAL

-A-

precautionary dianhydrides are pyromellitic dianhydride, benzophenone-5, 3 ', 4,4 * -tetracarboxylic acid dianhydride and the dianhydrides of liaphthalenetetracarboxylic acids.

If desired, anhydrides can be of those mentioned above Species which, however, have one or more substituent groups contain, e.g. halogens, v / ie in. certain dichloro and tetra-A chloronaphthalene derivatives.

Suitable anhydrides which contain heterocyclic rings with aromatic properties are those which those of furan, ihiophene, pyridine and pyrazine compounds. are conducted, e.g. 2hiophen-2,3,4,5-tetracarboxylic acid anhydride and pyrazine-2,3,5,6-tetracarboxylic anhydride.

Examples of the diamines are m-. and p-phenylenedianines, 2,2-3is- (4-aminophenyl) propane, bis- (4-aminophenyl) inethane, 5en- ™ sidin, bis- (4-arainophenyl) sulfide, bis- (4-aminophenyl) sulphone, 3is- (4-aninophenyl) ether, 1,5-diaminonaphthalene, 3,3'-dir. ethylbensidin, SjS'-Dinetlio ^ benzidiii, 4,4'-diaminobenzanilide and 2,6-dianinopyridine. Bic- (4-ar.inophenyl) ether and bis- (3-ar.iino-tihenyl) -sov; ie BIc- (4-ar.inophenyl) sulphones are very suitable and can, if desired, be used in combination.

The aromatic polyimides I are generally insoluble and infusible or have a high melting point, even if both C groups II and R ¹ are aromatic radicals forming bridges. These

009850/1967 Λ

BATH ORIGINAL

Properties are desirable for high-temperature applications in articles made from polyimides, but the manufacture of such articles is correspondingly difficult Coating of surfaces or sun impregnation of reinforcing materials or fillers, e.g. glass, asbestos or carbon fibers. The polyamic acids, however, are relatively unstable, ^{beginning to decompose above about 60 0} G, and the dipolar aprotic solvents commonly used to dissolve them (e.g. !!, N-dimethylacetamide) are expensive and quite toxic.

It has now been found that mixtures of (i) aromatic letracarboxylic dianhydrides or the corresponding dioders 2etraesters and (ii) urethane or urea derivatives of aromatic diamines and soluble and fusible prepolymers obtained by reacting (i) and (ii), valuable Intermediate products - used to make polyimide articles. The relative molar amounts of (i) and (ii) are preferably in the range from 2: 1 to 1: 1. For example, there can be up to a 50 molar excess of anhydride, however the diamine derivative is preferably not in excess.

The dianhydrides and diamines are as described above. The urethane and urea derivatives have the general

009850/1967

BATH ORIGINAL

- ο -

Z- - CO -HH - R ¹ - ITH - CO - Ζ »

in which "J has the meaning given above", Z and Z ^{1 are} groups of the formula -OY or 2TYY ¹ - and Y and Y ^{1 are} aliphatic or aromatic radicals, free of terminal or pendant ethylene groups, where Y and Y ¹ together with Your 17-aton are also able to form a heterocyclic ring (e.g. pyrrolidino or piperidino).

Mixtures of the dianhydrides or di- or .Tetraester and the

Urethane or urea derivatives of diamines melt in

geneinen at temperatures below 200 C, and sometimes at such low (temperatures such as 120 ° to 13O ⁰ C (depending on the nature of the connections), and they react to form a prepolymer with evolution of carbon dioxide (as well as an alcohol or phenol has evolved from urethane and a secondary amine of urea groups) to up to 95 $ of carbon dioxide theoretically available. hit the Urethanderi.vaten is usually a clear melt 'at 180 ⁰ C to 20O ⁰ C formed. with urea derivatives, the response appears faster to be, and a temperature of about 12O ⁰ C may be adequate. in principle, the reactants are heated to a suitable temperature to obtain a clear, (soluble or fusible) resin to drive so far without the reaction that the resin is made insoluble.

ORIGINAL

009850/1987

• ■ "

Reaction is possible in the melt (for example in a chivcekunreaktor) ;, 'however, it is more soluble, t.; T: v.cl2oarcr Yorpoly:.: Erer often advantageous, a slurry; r ccr lioaktionskcinpcnenteii in an inert liquid VerülLVxr-ur.scn: it ^J ; el, v / ie to form a hydrocarbon, and a uniform heating of the Eealrsionsgenic demand during the cutting zxx. It is particularly useful if the diluent is selected so that it is almost completely distilled off in the reaction point in which the reaction to form the prepolymer is complete. 2z ic-c also possible for this purpose a relatively non-reactive solution3 ::. Ittel for one or both of the reaction components, v; iü Kc «on. or to use an ester (e.g. 4-methylpentan-2-one or allyl acetate). Further, a reactive solvent such as an alcohol can also be used. In this case some of the alcohol reacts with the dianhydride to form the diester, and the latter reacts with the diamine derivative to form these prepolymers

In order to obtain a soluble prepolymer that can still be scratched give, the reaction is stopped when a relatively small! •! close (E.g. 5 to 10 ^ of the theoretically possible length of Koh-. lendioicyd is removed from the urethane or urea groups, because the prepolymer is then not only in highly polar solvents, v / ie tertiary amides (e.g. H, IT-Dinethylacetanid), sulfoxides (e.g. Dinethylsulfoxyd) and sulphones (e.g. 1,1-Dioxothiolan)

00 98 50/1967 bad original

-s-

is freely soluble, but often also in less highly polar ones and less expensive solvents such as ketones and cyclic jithers (see p. acetone, tetrahydrofuran, dioxane). Solvent, of medium polarity, such as nitriles (e.g. acetonitrile), esters (e.g. ethyl acetate) and haloalkanes (e.g. chloroform) also used v / earth.

With prolonged heating, especially at higher temperatures, more carbon dioxide is generated; developed and ground, insoluble polyimides are formed. Heating for one hour at 220 ^° C. may be sufficient to give a solid product at this temperature, but further thermal curing, as described for the polyamic acid products, for example in the above-mentioned British patents, is desirable in order to ensure full development of the o to achieve characteristic resistance properties of the polyimides.

It is possible that some reaction takes place before ICo hl end i oxide ^ is developed, however, the mixtures of the reaction components are immediately on melting even at 13O ⁰ C: yellow, with perhaps some units of the structure as

co

CO

^Z 'BAD ORIGINAL

009850/1967

with similarly structured Qligomers result. There is a hint from infrared spectroscopy that some anhydride rings still exist are present in the freely soluble prepolymers * However, the practicality of prepolymers does not depend on the accuracy such ideas regarding the chemical reaction pathways in question.

The presence of some insoluble polyimide fraction in the soluble prepolymer is not necessarily undesirable, as it acts as a filler in the intermediate stages and finally reinforced the finished article.

The lower the molecular weight of the radicals Z and Z ^r , the faster the reaction to form the prepolymer and then the polyimide. For this reason, urethanes and ureas are the formulas.

CH ₃ O-- CO - IiH - R '- IH - CO-

C ₂ H ₅ O - CO - HH - R ¹ - IJH- CO - OC ₂ H ₅ and (GH ₅ V ₂ H ¹ - CO - ^ HH - R ¹ -HH - CO -

generally preferred (where the meaning of R 'and the examples and preferred meanings therefor are as described above for the diamines HgB-R · -EH ₂ ). However, it is sometimes desirable to complete the polyimide ring closure

009850/1 967 BAD ORIGINAL

- ίο -

delay, for example to maintain the coherence of the object during the curing stage, and to this. Zv / eck can have at least 'some of the radicals Z and Z' a higher one Have Koiekular weight. The phenols, higher alcohols or higher secondary amines derived from the urethane or the urea groups released v / ground can also be an advantageous softening "effect on the prepolymer during this w conversion to polyimide. This is how urethanes and ureas, the higher groups, v / ie phenoxy, isooctyloxy and dibutylamino and can be used in any desired proportion with the faster reacting lower urethanes and ureas are mixed. ■

The melted prepolymers and even the melted ones Genetic of dianhydrides and urethanes or ureas according to Invention can be used directly for impregnating and coating or on the basis of fertilized molded objects before the polyimides are obtained Hardening stage can be used. The fusible materials can be used for molding, and fillers can be added with if desired to be incorporated into the initial reactants or to the prepolymer upon melting or added in solution in a volatile solvent. In this way, e.g. preformed polyimide powder can be used as a filler added to ground and brought into a malleable state, and the structure reinforcing fillers, such as Glass, asbestos and carbon or metal fibers can be added. Abrasives or solid lubricants (2Γ.Β '.

Graphite and Iolycdändisulfid) can be used as fillers for the manufacture from . 2olyinid objects used v / erden, uri as IIcer ^ crr.peratur-G-IeitinatGrial or self-tapping bearings too those.

The prepolymers are also valuable in solution casting, icing. or impregnation or for the incorporation of / fillers. "The prepolymer obtained is usually dissolved after about .5% oily development of carbon dioxide" at 10 to 20% solids. V. ^r fa flüchtigeg and inexpensive solution agent is required, acetone is particularly suitable. Purely for some purposes, see 3. Sun coating of wire is a relatively non-volatile solvent, like 'i-methyl-2-o; copyrrd.idin from Ifutaen and Kanr. -Either used alone or in a more volatile form in combination with solvents. The development of carbon dioxide and other non-corrosive volatile materials, v; ie alcohols, from the prepolymers during the hardening process offers a simple route to polyanide fences, which are valuable high-temperature insulation criteria.

The prepolymers or simply genes of the dianhydrides or Di- or tetraesters and urethanes or ureas according to the invention can be partially hardened by heating in such a way that most of the volatile material ($ 70 to $ 5) has evolved. The solid formed "can then to a fine powder ground and the latter at roughness temperature

or slightly increased barrier and high pressures (e.g.

009850/1967 bad ORIGINAL

v / otherwise up to 700 I-Hl / in) shaped v / ground. The molded bodies formed are strong enough for easy handling and can be sintered by heating in the free state, during which they develop their full strength. ■■ '^; ·· '■■■ - ■ "■' ■

The urethanes and ureas according to the invention are light accessible through the reaction of diisocyanates ^ ■ ■

OCII-R '-ITCO

with aliphatic or aromatic hydroxy compounds HOY or secondary amines HITYY '. Alternatively, the diamines' H ₂ H - R ¹ - M ₂ can be reacted with chloroform esters Cl - CO - OY to give the urethanes directly.

The invention is illustrated by the following examples.

Il

example 1

An equimolar mixture of 8.7 g (0.0270 col). Benzophenones, 3 ¹ , 4,4 '.- tstracarboxylic dianhydride and 10.0 g (0.0270 Hol) bic-C ^ isopropoxycarbonylaminophenyliethan

₅ ) 2 ~ O - CO - ire- ^ jV- ^CH 2 ~ ⁷ € ^ ~ ^lm " ^C0

was Kahler of the two solids produced together and melted at 145 ° to 15O ⁰ C. The mixture was stirred at '170 ⁰ C

009850/1907

'melted and the temperature was increased to 200 ⁰ G over 20 minutes. , Gas began to develop a look at about 19O ⁰ G. The temperature was maintained at 200 ° to 210 ⁰ C for 20 Hinuten; then the yellow liquid was poured from the reaction flask and heat set to a brittle yellow pest. This prepolymer was freely soluble in acetone, and it uses v / urde sum impregnating glass cloth by pressing at 3QO ⁰ C for 40 minutes under a pressure of 10 to 20 m / m, a solid, non-porous cured glass-filled polyimide product revealed. -. . -

Example 2

The procedure of Example 1 was repeated using 0.1 moles of each of the Eeaktionskoinponenten and increasing the temperature you 1? G 0 ° to 220 ⁰ C in the course of an hour (12 minutes the temperature was about 210 ⁰ C during e'twa) . The prepolymer was much less soluble in acetone than the product of Example. 1 (less than $ 5) »was freely soluble in NjF-Dimethylacetaaid. Analysis of carbon dioxide evolved (o theoretically possible total conversion from the urethane.

-H-

Example 3

A mixture of 103 g (ο, 32 Hol) 3enzophenon-3,3 ', 4,4'-tetracarboxylic acid diahydride and 109.4 g (ο, 32 Hol) sis- (4-ächo: £ 7earbonylaminophenyl) methane vmrde carefully in ground in a mortar and melted under nitrogen. The temperature of the melt was raised to 200 ⁰ G and held for five Hinuten in this order, and then the liquid was poured from the Heaktionskolben and cooled. 191.5 g of a brittle yellow resin was obtained and this yielded Mcht 3% w / w solutions in acetone, tetrahydrofuran and 1-methyl-2-oxopyirolidine. '■. · '

Example 4

A resin made from 72.7 g (0.33 mol) of pyroaellite dianhydride and 114 g (0.33 Mt) I) 3is- (4-ethoxycarbonylaninophenyl) nethane, as described in Example 3, prepared. 2) he obtained reddish-yellow Pesticide (163.0 g) easily gave 30% Gev /./ Gev; .- solutions in acetone, tetrahydrofuran, methyl formate ,. Acetonitrile and 1-He thyl-2-oxo pyrrolidine. .

Example 5

. A mixture of 145.3 f (0.67 Hol) T ^ romeilithdianhydrid and 114 g (0.33 mol) 3is- (4-etho; qycarbonylaminophenyl) methane

urcLc sor ~ iälti ~ ground in an Iorser and. under embroidery

The lard was ^{heated to 200 0} G and

; Ci cLiccer CJo ^ pcratur 10 I held for minutes to obtain a clear ict ^ slze, which was poured from the reaction flask and elcLihl ".. The reddish-yellow resin obtained (214.6 g) gave a slight one 3C ^£ ^ owned Gew./Gew.-Lösung in T-Hethyl-2-oxopyrrolidin.

Zin Mars was made from 72.7 g (0.33 hol) pyronellite dianhydride, 53.5 g (0.117 mol) 3ensophenor: -3.3 ^f , <, A- '-t atracarlic acid dianhydride and 114 g (O> 33 I-Iol) 3is- (4-ethoxycarbonylaninophenyl) -ne'th'aii, v / ie in 3eicpiel 3 besc-irisben. The reddish-red resin obtained (137 g) easily gave 305% Gev /./^ ev; .- solutions in acetone, tetrahydrofuran and i-methyl-2-oxopyrrole-dine.

Example 7

Sin resin was made from 107.3 g (0.53 Hol) of benzophenone-3,3 ', ^ ij ^ '- tetracarboxylic acid dianhydride and 84.0 g (0.53 Hol)' 1,3-M (äthojQrparbonylanino) benzene

₅ Η _Κ . 0. CO. HH- ^ V-HH. CO. 0. C ₂ E ₅

as described in Example 3, prepared. The received brown hars (173.7 g) gave 30% w / w solutions in Acetone, tetrahydrofuran, methyl formate, acetonitrile and 1-

I-: eth.yl-2-oxopyrro3iaine. - '.... ■■

009850/1987 pad original

Example "6

A liars was made from 72.7 g (0.33 Ιΐοΐ) pyronellite dianhydride and G4.0 g (o, 33. ί · Ιο!) 1,3-Di (ethoxycar "bonylamino)" benzene, such as in Example 3 "described. The resulting blood-red Resin (14-1.2 g) gave 50% w / w solutions in acetone and tetrahydrofuran.

Example 9

lin resin was made from 107.3 g ( ^{0.33 Hol) benzophenone-3,3 ', 4.4 l} -tetracarboxylic acid planhydride and 115 g (0.33 Hol) BLs- (4-ethozycarbonylaninophenyl) ether

C ₂ H ₅ -O.CO.HHr ^ y 0

_25th

v / ie described / produced in Example 3. The '· m-brown resin (189.3 g) 3O5Sige Gev /./ weight solutions obtained in CETR hydrofuran and-i-Hethyl-2-oxopyirolidin.

Example 10 . .

A resin was made from 73 g (0.33 hol) of pyroneliite dianhydride and 115 g (0.33 Hol) bis (4-ätho ^ ycarbonylaminophenyl) ether, as described in Example 3, prepared. The resulting blood-red resin (176 g) gave 30% w / w solutions in tetra hydrofuran and 1-He "fc-hyl-2-oxo pyrrolidine.

009860/1987

Example 11 "

± iin2 Auischlännung of 107.3 g (ο, 33 mol) benzophenone-. 3,3'-4,4 ^r -t3tracarboxylic acid dianhydride and 114 g (0.33 hol) 3is- (4-ethoxy ^ 7carbonylaminophen5'-l) methane in 200 cm × ³ × 4-methylpentane-2-onvmde stirred under nitrogen and heated, the solvent being quickly removed by distillation. When the solvent was almost completely removed, the temperature of the reaction mixture was increased to 20O ⁰ C and held there for 5 minutes. The melt was then poured out and cooled to a yellow resin (212.4 g) which easily gave 30% w / w solutions in acetone, tetrahydrofuran, acetonitrile and i-ethyl-2-axQpyrrolidine.

Example 12

Sin resin was as described in Example 11, and with prepared the same reaction components, except that 200 ca amyl acetate is used instead of 4-methylpentan-2-one became. The resulting yellow resin (222 g) easily yielded 30% W / W solutions in acetone, tetrahydrofuran and 1-1'Iethyl-

■ ν

2-oxopyrroleLdin. ■ ■ '

'■ " Example 13 / -

A resin was described in Example 11 and produced with the same reaction components, "" 'except for V. that 200 cm of butane-1-oil instead of 4-methylpentane-2-one ver.

0098 50/1987 BAD ORIGINAL

was turned. The resulting pale yellow resin (241.9 g; yielded slightly 30% w / w solutions in acetone, tetrahydrofuran and 1-methyl-2-o; co-pyrrolidine.

- Example 1 4

A resin was obtained as described in Example 11, using 107 g (o, 33 I-Iol) benzophenone ^3,3-1, 4,4-t3tra ~ cärbonsäurec.ianhydrid, 123 "g (o, 33 Ιίοΐ ) 3is- (4-i3opropo :: ycarbonylaiiinophenyl) nethane and 23δ cm m-xylene prepared The yellow resin obtained (190 g) easily gave 30% weight / weight solutions in acetone, tetrahydrofuran and 1-kethyl -2-o: -: opyrrolidine. ·.

• Example 15

A mixture of 107 g (0.33 liol) benzophenone-3,3 ', 4,4'-tetracarboxylic acid dianhydride and 102 g (0.33 KoI) 2,4-bis- (H' ·, U ¹ -di-n -propylureido) toluene

(C ₃ H ₇ ) ₂ 1T. CO. HH ^ _1ΊΗ. CCIi (C ₃ H ₇ ),

I ₃ S ^

was carefully ground in a mortar and melted under nitrogen. The mixture was heated at 12Q ⁰ C and then allowed to cool. The obtained resin (197 g) yielded easily

BAD ORIGINAL 00 9 8 SO / 1187

ir-3 3ΟΪ-ΐ £ Θ. Gev /./ G-ev /.- solution in 1-: Cethyl-2-öxopyrro: ± din, one C ^ solution in! Zetrahydrofur & iv and a 15% solution in

Example 16

Sin resin was, as described in Example TT- ", using 54.4 g (o-, 20 mol) of benzophenone-3,3 ¹ , 4,4'-tetracarboxylic acid diantihydride, 78.4 S (c, 2 LIoI) bis- (4-ethoxycaroonylaainop'aenyl) sulphone

C ₂ K ₅ .0. CC. HH - ^ "^ - DO ₂ -. ^ J ^ - ΙΠϊ. CO. O. C ₂ H ₅

and 150 cn ³ 3utane-1 oil. The yellow resin obtained (147 g) orgao easily a 5Ci? Ige wt / uev /. Solution in 1-methyl-2-oxo pyrrolidine. -

Example 17

A .Seraisch of 1030 g (5.2 Hol) benzophenone-3,3 ¹ , 4,4'-tstracarboxylic acid dianhydride and 1094 g (3.2 mol) bis (4-ethoxy-. CarbonylaninophenyDnethan v / urde carefully in one Körser genahlen and passed through a glass screw reactor at 20G ⁰ C. the melted Genisch, and a clear yellow Earz flo3 of .the reactor. the estimated Verv / express time of Reaktionsge-Tiisches in den.Reaktor was 5 to 10 Hinuten. the obtained

OO98S0 / 1967

brittle yellow resin (2064 g) easily gave a 30% w / w Ge-v /. Solution in acetone.

Example 18

665 g of a sample as in Example 17, "resin produced was heated in nitrogen at 300 ⁰ C for 40 minutes. The brown solid obtained checkout (532,5g) was cooled, ground and sieved in a Hörser ■ (opening size o, 045 in In each case 1.0 g samples of the fine powder obtained were pressed into disks with a 19 ram pressure gauge in a hardened steel mold at low temperatures and pressures of up to 700 HL7 / n Time increased by 3 minutes, held at this value for five minutes, and then decreased.

The ^r to this V. discs else obtained were to use strong and light were sintered by heating in freiein state in air at 5O ⁰ G at 35O ⁰ C in the course of 9 hours "Solid brown moldings were obtained in this manner, v. And their shear strength was determined by a punch and a technique with a die and a cylindrical punch with a diameter of 3.2 mm.

BATH ORIGINAL

009850/1967

■ - 21 -,.

P-reSdruck Gev / icht ^ Hclust νΐΓα.- Density of the shear strength I'27 / n2 - '"rend des üinx.erns disk after the finished

> ^c p the sinter
s / crP , ormxings .. • 275 6.4 ' 1.26 m
64.1 410 ; 6.4 1.29 71.7 550 - 6.2 1.30 '73, 6 690 6.6 1.31 84.1 Example 19

A mixture of 10.9 S (o, o32 HoI) 3is- (4-etho; <ycarbonvla: .äno ^ henyl) methane and 10.3 g (o, o32 mol) J3en2ophenon-3,3 ', 4 , 4'- tcitracarbonsäuredianhydrid vmrde carefully in a mortar ground and then heated at 3OQ ⁰ C for 40 minutes in .Luft. The brown pesticide obtained (14.7 g) was ground in a mortar and sieved through a sieve with an opening size of 0.045 parts. .

Samples of 1 g each of the fine powder obtained were pressed onto disks at a pressure of −700 IW / m and these were sintered as described in Example 18. The density of the disks was 1.07 g / cm and their shear strength was 34.2 M / m ² . . ■. '■■■: -.'. ■ ·. ■ '■ -. "■ ^; -:"■■' ■ ■

- Example 20

An asbestos felt; was made by dispersing 60 to 70 g of fine asbestos fibers (chrysotile): in about 3 Mt of water and filtering

S860 / 1S6? BADORiGiNAL

- 22 .-

the resulting Aufüchlär.i; r.ung through, a fine rust-free steel gas sieve ("18.cn ze 35 cn) produced., The moist mushroom obtained was first at 50 ° to 60 ⁰ O and finally at 200 ^° C. for 18 hours.

The raw edges were trimmed off from the felt, with a hatching. resulted in a weight of 63.0 g. This had been impregnated with 6 og of the resin as described in Example 3, dissolved in 150 cn acetone. Dried off at Eaur. '. t. temperature. The impregnated had been in then, prebaked 200 ⁰ C for 60 minutes.

Rectangles (15.cn χ 5 cn) were obtained from the. Pornnatte cut, and four such rectangles, weighing 4-5 g, were placed in a senipositive steel mold (15 om χ 5 cn)

and at a pressure of 2.5 I-IIT / n and gepre3t a temperature of 225 ⁰ C for 20 Hinuten, and then the SenOeratur was on

ο '

^ 300 C increased for more than 20 minutes. The porn was cooled in the press and post cured by heating in a free state in the air at 80 ⁰ C to 350 ⁰ C in the course of new hours. . ".,.. ■ ■

. The resulting solid coherent brown Pormlcörper _"possessed, the I € aces 14,95 cm χ χ 5.00 cm 0.33 cm to 0.36..

BAD ORlGifW.

0088 50/1967

2i: i resin was made from 4-G3 g ("'» 5 I-Iol) 3enzop.hen.on-3,3', 4, 4 ^f - - ^ ■ _u _'j.carVcnüUuredia: ihydride and 555 C ( '»5 I-Iol) 313 - (4-XS-O- ■ ₁ : rc :: D; ^ - carccr-7la".ir.cp'ienyl) rie-j: ia: a, as in Example 3 .beschriel.er .., herjeo-ellt and to one:.; ground fine powder. A piece of this Iarapv-verse and 50 g of fine v / ice ace-

::. is.c.i au

"5

ce-'jcs v.-arc.e sorjf.alui ^ G ⁰ -'- ⁰⁰ '"-! 3CC cn acetone v / urden hln z - ;. ze ~; e ce ::,, and the paste'v / . urda Troclrnen initially left in air Z ± z eriialtciien solid IZluir. e: iv / ere at 200 ⁰ C '50 liir.uten long before eliärtct ~, '■ ßelzi'cZ-z', powder wobbles and through a sieve! nit cir.er üfrnunjs ^ röie of 0.5 nr.gesciiiclct.

vSo a Prcce deg Per;.: powder vrarden to a 15 ca χ 5 C-. . 21ε "" te Found ORNT and letctere v.'urde, v IU ceeciirieoen in Example 20 na c hg ε et hard 2er obtained solid kohärtente Porja-.

2 '

linsal had a 3iege-I-Iodul of 13.5 G-IT / ri.

3eisp; .el 22

A layer of 27 g of aligned carbon fibers (Courtauläs-iTyp 3) was nit 30 g of the prepared as in Example 1, impregnated in resin dissolved in 100 er / acetone. the The mat was dried in air and at 200 ° C. for 30 minutes pre-hardened. ■

Pieces of the impregnated hat obtained were in a 15 cm χ 5 cn - seniipositive Stalilforn with the passages ccv / staggered lengthways and yours arranged. The sample was then

009850/1967.

at 21O ⁰ C and 203 1Π / η ² v / hile 20 I-Iinuten and then at 500 ⁰ C 'and 6.2 I2i / a compression molded for a further 20 I-Iinuten. The molded body / was cured by -Hr hi te s of 230 C to 400 C in the course of zv / ei hours and holding the Formkc'rpers / at 400 ⁰ C for 30 Hinuten. The finished molded body obtained was solid and coherent and contained about 62 carbon fibers. Her Eiege-Hodul "was 115 G £ * / zi

Example 23

19 g of glass cloth were mixed with 30 g of resin, as in Example

1 and was dissolved in 50 cm acetone, impregnated. The 'latte! Was precured in air and then dried at 200 ⁰ C for 30 minutes. Pieces of the resulting impregnated had been cut so that they c in a 15: 5 c cn - fitted seraipositive Stahlforn- and at 210 ⁰ C and 2.8 Iü7 / ri during 67 liinuten and then at 300 G and 6j2 M / n while Pressed for 20 minutes. The molding was post-cured as described in Example 22. The finished molding was strong and coherent.

The invention has been described above in terms of mixtures (i) aromatic letracarboxylic dianhydrides or the corresponding Di- or tetraesters and (ii) urethane or urea derivatives of aromatic diamines and soluble and fusible prepolymers which are obtained by reacting (i) and

BATH ORIGINAL

009850/1967

(ii) can be obtained. According to the invention can be described benen mixtures of - (I) and (ii) completely or partially by urethane or urea derivatives of amino-aromatic Licarboxylic anhydrides

Z-CO - ITII- H "

or the corresponding ϊΐοηο or diesters are replaced. In this formula, Z has the meaning given above and R "is a trivalent radical with aromatic properties with the carbonyl groups in the ortho or peri-position to one another, similar to the above-described II and PJ (with preferably at least some bridging aromatic radicals For example, ^ -etho ^ carbonylaninophthalic anhydride and 4- (4-etho; xycarboiiylaminopheno'xy) phthalic anhydride can be used.

BATH

009850 /

Claims (1)

Claims 1)? Olynerizable substance from (a) a G-enisoh. from (i) an aromatic Ee ^ racaroonsäuredianhydrid äer.Pormsl χ. / or a corresponding di- or setraester and (ii) one. Urethane or urea derivative of an aromatic. Dianin's the general Porael . Z-CO-IH - R ¹ - ITd - 00 - Z ¹ ; or (b) a urethane or urea derivative of an amino aromatic dicarboxylic acid anhydride of the formula .οο _χ Z-CO-IiH-H " ^X 0 ^ CO ^ or a corresponding hono- or diester; or (c) a prepolymer obtained by reacting (i) and (ii) or (Ta), Y / o "oei in the formulas R and R"jev; eils four-part ”or three-part esters of aromatic Characteristic with the Carl donyl groups in ortho- or peri-alignment to one another, R ¹ a zv / one- BATH ORIGINAL 00 9850/1917 'v: crtI ~ he cor Zest of aromatic YJigenart, Z and Z ¹ groups or -OZ 7or.:;gZn -ITYY represent ^1, and Y and Y ^f alipahtische :: c -; '.-- lcr.3r-ap -_: e: i cind, wocoi Y ur.d Y' Susannen nit den IT-Atoc cn dl capable of forming a heterocyclic ring 2) Poly-icrisiercare Succtan; ·; according to claim Λ, characterized in that at least some of the radicals R, R 'or R "crüclrenciidende aromatic radicals, derived from compounds of the I? orr.: el are, v / or in X -0 ~ ,. -S-, -30-, -SO, -, -, -00-, -COIiIi-, -CII ₉ - or -G (CH ₅ ) ₂ - is, ■ -. ■■ '■ 3) Polymerizable © Susstans according to one of the M vorhergehen- claims, characterized characterized gelcenn-, ä.o.2 Pyroraellithdianhydrid the dianhydride and / or 3,3-Senzophenon ·, 4,4 '-t etra-' dianhydride is. 4) Polymerizable substance according to one of the preceding claims,. 'Characterized in that it is a cutable Äcuinolares G-enisch from an aromatic "etracarbon-" acid dianhydride and a urethane or urea derivative one BATH 009850/1967 aromatic diamine or a soluble or meltable prepolymer obtained therefrom. 5) Method of making a prepolymer, thereby characterized in that (a) a mixture of (i) an aromatic dianhydride or a corresponding di- or tetraester ' ui-ά (ii) a urea or urethane derivative of an aromatic • see diamines or (b) a urethane or urea derivative _ Amino-aromatic dicarboxylic acid anhydride or a corresponding one Mono- or diester according to claim 1 heated until up to 955 * of the theoretically available carbon dioxide develops have.- ■. 6) Method according to claim 5, characterized in that that a fusible equimolar mixture .aus an aromatic Tetracarboxylic dianhydride and a urethane or urea derivative of an aromatic diamine at 200 C or above 9- ■ - ■ - ■, ■ ■■■ ". - ■■ * ■■■ ■ ··. '. · melts. ---.__ '. - ?.) Method according to claim έ, characterized by the Working method yp'n example 1 or example 2. 8} The method according to claim 5, characterized by the Working part of examples. 3 to 19. 9) prepolymer prepared according to claim 5 or claim 8. .- '"■. - -" "· 009850/1967 10) prepolymer, prepared according to claim 6 or An. Proverb 7.. '. 11) prepolymer according to claim 1 to 3 or claim 9 » characterized by a content of a reinforcing filler. . 12) prepolymer according to claim 11, characterized in, that the filler is polyimide powder. 13) prepolymer according to claim 11, characterized in that that the filler is glass fiber, ''.-..- .. 14) prepolymer according to claim 11, characterized in that that the filler is asbestos fiber. 15) prepolymer according to claim 11, characterized in that that the filler is carbon fiber. 16) prepolymer according to claim 11, characterized in that \ the filler is metal fiber. . • ■ · 17) prepolymer according to claim 10 ,. marked by· the working procedure of examples 20, to 22 .. · ■ OOS85071WT 1ü) prepolymers3 according to one of claims 11 to 15 * - characterized in that the prepolymer is a prepolymer according to x \ nspruch 4 "or claim 10 is. 19) Hardened insoluble and infusible polymer Material, characterized in that it is obtained by further heating a prepolymer according to any one of claims 1 to 3, and 11 to 17 is obtained. 20) Hardened insoluble and infusible polymeric material, characterized in that it is obtained by further heating of a prepolymer according to claim 4 ». Claim 10 or is received. BATH ORIGINAL ijtr