DE1595080A1 - Process for the production of polyimides - Google Patents

Description

Patent attorneys

DRYING. WALTER ABITZ DR. DIETER MORF

Monks

Dr ₀ Expl.

October 30, 1964

■ B · I. ■ DU ■ BONT, DE HEMOUSS ANJ) COMPANY 10th and Market Streets, Wilmington 98, DeI ₀ , USA

Process for the production of polyimides

The invention "relates to a composition suitable for the production of a new class of polymers, the = special it relates to a new class of polyimides with unique features ₀

According to the invention, polymers are created which through the repeating structural units

I!

ti

η O

11

Ö.

A \

Il.

Il

Il

Il

0 0 9 8 13/1796

_BA O

denote in which R ₁ , Rg ₉ ■% »^ 4» ^ 5 * ^R 6 are the same or different, with the exception of the / exceptions given below; the radicals can represent aliphatic, aromatic, carbocyclic or heterocyclic radicals or they can contain one or more such radicals ^ At least one of the radicals R ₁ , Rg, R *, Ra, He »Rg and R« must be an aromatic keto carbon atom (- C-) which is directly connected to a = N <~ Rg-> N = group, thereby forming the group C ^ H-Rq-N «o The carbon atom in the latter group connects an aromatic ring directly to another carbon atom The unsaturated stick material bonds specified in the latter group are linked to an adjacent unit in the polymer, for example by binding to another aromatic keto carbon atom in another RJ "" t radical or to a pair of carbonyl groups in an adjacent unit of the polymer to form an imide ring , corresponding to pairs 1, 2 and 15 »16ο

In the above formula, the remainders R _1s Rg ₉ R * and R ^ are organic radicals, S where the carbonyl groups 1,2; 3,4i 5 »&; 7 * 8; 9.10; 11.12; 13.14 and 15.16 are directly attached to adjacent carbon atoms o Preferably the radicals R ₁ , Rg $ R% and R ^ are aromatic radicals o It is for one

009813/1796

FPD-1765 ^

Skilled in the art obvious _t that the anhydride end groups can be hydrolyzed to acid groups which in turn partially or totally esterified werden.können, and that the sequence of bracketed units in the obigen.Formel regularly or unregelmäasig may be what depends on the properties of the reactants, the The designations χ and y are integers which reflect the number of units in brackets Value χ is always at least 1, usually large; y is usually at least T, but theoretically O can be. From a practical standpoint, both χ and y are usually large, integers? Accordingly, a simple implementation comprises only two reactants, for example the ethyl diester of 3-, 5 * , 4,4 ^f -benzophenone tetracarboxylic acid and 4 * 4 ^l = oxydianilino

Have R ^ ₉ Hg »R · * and R. the Psrmel

U " ^G " LC U

BATH ORIGINAL 00 98 13/1796

G,

and R _{8 has} the formula -

the parenthesized unit ζ can be the same as the bracketed unit y and you can get a product with the relatively simple structural formula

Il

Establish - in which - the unsecured bonds
the nitrogen atoms serve to crosslink the structure shown with another unit of the polymer

0098 13/1796

763

By increasing the amount of oxydianiline used, one or both of the oxygen atoms marked with asterisks can be replaced by a Φι ^ ΦΓ *; ί-1ί = -Εβ8ί 'for further crosslinking of the polymer ^ It is noted that in formula (2) every linearly recurring unit (within the brackets), through the «Ν ^^ / ^^ - Ο-λ ^» · - !? » "—Group is cross-linked", Normally some of these units are not cross-linked.? Instead of the "Ternefczungsgruppe simply contain an ⁿ = 0" group o The amount of diamine used determines the degree of degradation; at least about 20 $ of the units in brackets in formula (1) are networked to

As used herein the term "aromatic keto ^ carbon atom" refers to a keto carbon atom (C-), which is directly attached to an aromatic ring carbon atom and to another carbon atom, as in benzophenone and acetophenone the case isto The carbon atoms of the Carboxyl groups in the heterocyclic imide or anhydride rings of the above formulas are not aromatic keto carbon atoms o The terms "aromatic ring" and "aromatic radical" relate to rings and radicals that are aromatically unsaturated «, typical for the radicals Rj» R ₂ , R- and R ^ in formula (1) are the following 'radicals:

009813/1796

HHM? 6?

In the above radicals, y denotes the radical = 0, SxN-Rg-H * or sET-Rg-HHg; ^R q represents alkylene, arylene, and the like; R ₁₀ is an Alkylreat und.R ₁₁ is preferably an alkylene radical, but can also be any non-harmful divalent radical, for example arylene, -0-,

bath

009813/1796

FFB-1 763 Alkyl ~ O Alkyl ~ 0 - Alkyl
I. O - Si, - Si - O ~, P- O
η - S ~ • f ^ * S ■ ", Alkyl Alkyl O O or Alkyl
C. - Μ

The alkyl groups mentioned can be substituted by aryl, for example phenyl, be replaced ₀ As comes by the above formulas expressed represent the carbon atoms located in peri-position of compounds such as naphthalene and anthracene in the context of the invention, adjacent carbon atoms darο the by Rc, Rg , R »and Rq are divalent organic radicals that can be aliphatic, aromatic, carbocyclic or heterocyclic and are capable of forming a diamine o Typical such radicals are divalent radicals that correspond to the above-mentioned radicals R ^ ₁ Rp, R * and R _A correspond; they will go through

illustrates the following formulas:

Il

Y «I

-G-

= " 7

009813/1796

In the above best the radicals T ₉ Rq and H _{11 have} the same meaning as above; the bonus H inside a ring means that the ring ate saturated

The terms "alkyl" and "alkylene" used herein are preferably radicals with fewer than seven carbon atoms, but larger radicals can be used if the difficulty involved is not critical can also use larger groups ο Aryl and arylene groups substituted with alkyl and alkyl and alkylene groups substituted with aryl can also be used ο Each of the radicals R _1-11 can also include various non-harmful substituents, for example fluoride chloride, bromide, NO ₂ , COOH, COO-Z, where Z is alkyl, aryl, alkaryl, aralkyi and so on «

The polyimides according to the invention are crosslinked and are from an intimate mixture of one diamine and one The diester produced by a tetreearboxylic acid has the structural formula (the arrows mean isomerism)

8 - «bZ

009813/1796

FFB = I 763

HOQCT

in which R ^ _{2 is} alkyl or aralkyl »A represents the radicals -R * _A defined above, where Y is equal to 0, that is to say in the radicals R _{1 A} there are carbonyl groups instead of any amine-substituted keto carbon atoms (-C-) <, The biamine has the formula in which M represents a divalent organic radical like the radicals R _c «defined above, but in the radicals Rc ₇ there are instead of any amine substitutes Ke to °> carbon of χ atoms carbonyl groups (= ■ § «·)!» At least one of the radicals A or M contains an aromatic keto group. The diamine is present in the mixture in an at least 15 molar excess, based on the diester present. The components which contain the aromatic keto group are present in the mixture in an amount of at least 30 moles of the diester present before ο This mixture can be a solid mixture, if suitable measures have been taken, for example, grinding the solids to fine particles and then intimate mixing, = Yor solvent before ^ ± in which both components are soluble at ambient temperature or can be brought into solution by heating ο
>. = ':' _α 3AO. ORiGIMAi

~ ^y ~ 00 9 813/1796

S ¹ PD-1763

The above diester diacid / diamine solutions are preferably prepared "by reacting your at least one tetracarboxylic acid dishydride with a monohydric alcohol (preferably methanol, ethanol, propanol, butanol, benzyl alcohol) to form a monomeric diester diacid." on the basis of the following reaction of 3> 3 ^f _t 4> 4 * -Bön3ophenon-tetracarboxylic dianhydride with ethanol veransohaulicheno

Il

Reflux

. HH
J ₂ H ₅

“000

" ₍ vac .--- * ¹

-DOC

000 H

000-MJ

(4)

The bisester disMure can be prepared directly in a solvent suitable for the purposes of the invention, or it can be isolated first. However, the diester can also be prepared by directly esterifying the corresponding tetracarboxylic acid. Then the diester diacid is added at least one organic Diarain adds to the Dieater diacid / diamine Iösung herzusteilen _p in which the diamine #igen in an at least 15 tJber "

- 10

0098 13/1796

HIM 763. ■.

shot is present, based on the existing dietary acid

Preferably the dianin is in a 20 bit molar excess before * Usually results in calibration with a larger Diemin-surplus than 100 Äol- # no .. ' lorfceil *

The oil / diacid / biamin-loemig is stable for a long time and is in a very regular form but is converted into highly softening polymers according to the invention in a number of applications, for example as wire coatings, varnishes, adhesives, pollen (without! Carrier and on carriers ) and dergleiohene the Viecoaität the solution at a solids content of about 40 to 60 f is about OFI to 100 P, but for most Anwendungβzweckt it is adjusted by removal or addition of Lösungemitteln to give a suitable Yieoositat the solution for the particular application «

The esterification can be carried out in any convenient solvent that does not interfere with the reaction reacts inappropriately with the ester-diacid product " Liquids such as Ν, Η-dimethylformamide and 11, H-dimethylacetamide are preferred Other solvents that can be used according to the invention include »

11-

PI ¹ D-1763

ΙίρΝ-diethylformamide, H _r N ~ diethylaoetaaid _f Κ, Ν-dimethyl methoiyaoetamid, N-methylcaprolaetam, dimethylsulfoxide, N ~ methyl-2-pyrroliäon, tetramethylene urea, pyridine,
Dimethyl-Bulfon, Hexamethylphoephoraraid, Tetramethylene «εulfön, Formamid, N-Hethylformamid, Butyrolaoton tmd
N-ethyl-2-pyrrolidone, ketones, e.g. methyl ethyl ketone, nitroalkanes, e.g. nitroethane, nitropropane and so on. Toluene or cyolohezane, insert »

The tetracarbonic dianhydrides, which are two-dimensional as a starting material for the production of the invention Polyimides used have the general shape ice

M ti

0 O

in which A has the above meaning o To special, he «
Dianhydrides suitable according to the invention include pyromellitic acid dianhydride _% 3,3 ', 4,4'-diphenyltetracarbonic acid

12 -

00 98 13/1796

TOM763

dianhydride, 1 * 2.5 »e ^ naphthalenetetracarbonic acid dianhydride, 2 _t 2 ', 3,3' -diphenyl tetraoarboxylic acid dianhydride, 4» 4'-iso prepylidene-diphthalic anhydride, 4,4-sulfonyl-diphthalic acid anhydride., 3,4 , 9,10-Perylente traoarboneäuredianhydri d _f A ₉ 4 '-OxydiphthalBäiireanhyärid, 1,2,4 »5-carboxylic acid Haplithalintetra dlanhydrid, 1,4,5,8-Naphtfealintetraoarbonaäuredianhydrid _t 2,3,6,7-Naphthalintetraoarbonaäaredianhydrld, 3 , 3 '~ ~ isopyropyliden diphthaleaureanhydrtd, 3.3 * -ithylidwidiphtfaalsäureanhydrid, 4,4'-ethylidene ~ diphthalic, 3R3 ^<-Metbylen "diphthaleäureaaihydrid _# 4" 4 "-Κβ% 7ΐβη- diphthalic, Mellophsnsäurediauhyörld, _2.3} 5» 6-pyrazine tracarboxylic acid = dianhycl3fid, 2,3 * 4 "5-thiophene" tetracarboxylic acid dianhydride _? 4 _e 4'-biphthalic anhydride, 3 j 3'-biphthalic anhydride, 2,3,4,5 ~ pyrrolidonte tracarbonic acid dianhydride, 1,4 «bimethyl ~ 7j8 () oot-7-en-2,3,5, e ~ tetracarbonic acid dia» hydriä _f chlorbioyclo »(2 <> 2 ο 2) ~ o ct-7-en-2,3,5,
dianhydride, 7,8-diphenylbioyclo- (2 · 2 * 2) -oct-7 ~ en-2,3 »5 * fite traoarboxylic acid dianhydride, 1,8 ~ 3) i5ietiiyl-dioyclo- (2o2 _ei 2) -OO t- 7 = -en »2,3,5,6-1« tracarboxylic acid dianhydride _v 1,2,3,4-cyclopeiitane tetracarboxylic acid dianhydride imd ethylenetetraoarboxylic acid dianhydride o

Other useful dianhydrides also include the

BATH ORIGINAL

009813/1796

I ¹ PIM 763

3 1 3 '»414 · -Banzophenontetraearonic acid dianhydride and its isomers are as follows

where Rg and R ^ q have the meaning given above?

and the locations of these compounds as well as others

obvious ^ equivalents of this, for example such? the contain no harmful substituents.

The organic diamines which nan uses as starting material for the production of the products according to the invention have the structural formula HgH -H-

14 -

0098 13/1796

4Β

in which M has the meaning given above. Su particularly beTorsugten diamines include 4 "4 ⁱ -Isopropylidendianilin, 4.4 ^l methylene dianiline, Beneidln, 3,3' ² ^ OhIOiS-benzidija, 4,4 '- Phiodianilin _t 3.3 ^l sulfonyl dianiline , 4,4'-sulfonyl-dianiline, 4,4 ^f- oxydianiline _f 1,5-haphthalenylinftiamine, 4 _f 4 '- (diethylsilylene) -dianiline, 4 _f 4 * 4> ipbenylsilylenj-dianiline, 4 »4 ^t - ( Ethylphoephinyliden) -dianiline _f 4,4 * - (Phenylphoephinyliden) -dianiline, 4,4 '- (ST-He thylamino) -dianiline, 4,4 ^f - (N-Phßnylarainci-dieiiilin and mixtures. Thereof, m- phenylene diamine, p-phenylene diaaiin, 2,6-diaminopyridine, 4t4'-Methylendicyolohexylemln _f HexiM-methylenediamine, heptamethylenediamine, Ootamethylendiamis "nonamethylenediamine, De camethylendiamin and 1,4-Cyolohexandiamino

The steepness isomers of these compounds, for example the corresponding 2,2'-diamino, 5,3'-diamino and 3,4'-3) iamino compounds are also used as starting materials Usable In a similar way one can find diamines, which the have the following formulas, insert « O

BAD ORIGJNAt - 15 -

0098 13/17 96

These compounds do not know eohädlioh * substituents carry, for example halogen, hydrocarbon, alkoxy and Nitril-Grupperio

When carrying out the method according to the invention, it is important that one of the dianhydrides or one of the Diamines or both contain an aromatic keto group, by which a keto group (-C-) is meant which is bonded directly to an aromatic ring carbon atom on the one hand and to another carbon atom on the other hand, such as in bensophenone ^ tetracarboxylic dianhydride or in Acetophenone In addition, the aromatic keto group-containing dianhydride and / or diamine in the Reaction equipment in an amount of at least about 30 mol $ of all of the dianhydrides are present .. Usually lie 40 to 100 moles of the total diene hydrides and / or diamines, which contain the aromatic keto groups, if polymers are desired which are the most useful Properties have «In a reaction mixture, in which both the dianhydride and the diamine aromatic keto

- 16 -

0098 13/1796

■ KHM763 ff

groups should contain the total amount of. Components _f that contain these groups are present in an amount of at least 30 molar? S based on all dianhydrides present »

The diester-diacid / diamine / monomer solutions, which are produced according to the invention, are in an expedient form for direct application as insulating varnish or for the production of high-quality, molded structures which require rigidity and high dielectric properties * whatever the application is or will be used which geometric shape "the monomeric solution of Biester-diaäure / diamine is ssweokmäseigerweiee converted into the erfindungsgemäsaen polymers" by placing them initially about 200 to 10 minutes "at about 50 to 200 ⁰ C burns to ο TJM most products obtained one erhitat the solution after the Ponngebuag about 120 to 30 minutes at about 80 to 150 ⁰ C or while "until substantially all the solvent is removed and solidifies the mixture tight wirdο This" Torbrennen ¹ * helps in large part, the brittleness and to reduce the formation of ice in the final polymer to a minimum o Subsequently, one increases d ie temperature is converted 1000 to 1 * min to about 150 to 500 ⁰ O, preferably about 500 to 2 minutes »to 200 to 400 ⁰ G ₉ or until substantially all Diarain; the lower temperatures correspond to a longer time ο

₁₇ - SAD ORfGfISiAL

0098 1371796

FFB-1763 if

It is noted that the monomeric solutions according to the invention can be modified by giving them different ones monomeric or polymeric materials before or even after shaping into a desired shape, before heating admits ο in some cases you can get as much as 50 ^ or more Add modifiers ο of course you can also use inert ones Materials, for example pigments, dyes, organic and inorganic fillers, before or afterwards add to the shape =

Adhesive compounds based on the polyimides according to the invention are normally used as liquid adhesives, unsupported films or strips of film, the latter preferably being on a woven or non-woven glass fiber carrier. these tissues are preference "be as heat-cleaned prior to use, or a Methaorylatchromylohlorid-Pinieh have" After having impregnated a strip with the liquid Klebetoffmaeee "wJLrd the system for the removal of solvent is about 120 to * 30 minutes at 50 to 200 ⁰ C ₉ preferably pre-cured for 60 minutes at 10O ⁰ C ₉ to obtain a strip which is easy to handle and over extended areas tent

- 18 -

0098 13/1796

lagerbe constantly let <> If you want maximum resistance to storage, the strip can be stored in a cool place (0 to 10 ⁰ C) , Foils and turkey «lent fabrics made from high-melting synthetic polymers, for example from fully aromatic polyamides, from polytetrafluoroethylene and the like"

Adhesive masses from the polyimides according to the invention can be compoun'dieren with suitable insurance substances, for example with aluminum dust, powdered asbestos, aluminum oxide powder, iron powder, glass flakes, tin dust, zinc dust, zinc tetraoxychromate and chromium oxide o For special purposes it may be desirable to use mixtures of other resins with polyimides use, for example with Pkenolharzen, epoxy resins and silicone _e Stick "stoffharzenο It is desirable that the resins are compatible with each networked employed polyimides; however, they can form a chemical bond with the reactive groups of the polyimide. Suitable compatible materials include epoxy resins of the bisphenol type, for example "Epen 828", "Epon 1007" and other types of epoxy resin, for example the resin with the formula

009813/1796

HIM 763

OCH ₂ ο CH-OHg OOHg ο

which has an average molecular weight of about 500 and a Bpoxy equivalent of about 150 o Other suitable materials include bisphenol-A, epoxynovolaoke, polyphenylene oxides, bensoguanamine-formaldehyde haree, polyphenylenes, aliphatic polyamides, euo example Hylonharee, aromatic polyamides, sum example ii-phenylenieophthalamide and terephthalimide, polyester, for example hexamethylene isophthalate, polyesters containing oyanurate, polyvinyl formal, acetal and butyral resins, CuBaron-IndenharBe _9, polyacrylonitrile and aorylnitrile copolymers

Ss can also be used for special purposes It may be desirable to add heat stabilizers to the adhesive mass o examples of such materials are areenthioareenate, copper 8-quinolinolate, iron ohelate of 8-hydroxyquinoline, Eupfer diethylenetriamine dibromide, tri- (chloroethyl) phoephite, phenylphosphinic acid and arsenic pentoxydo

Biese Klebetoffmaseen are used for a variety of Substrates »In general, these are metals, such as

- 20 -

009813/1796 ^ _Gf ^

wise aluminum alloys, stainless steel «cold rolled Steel »Magnesium, titanium, copper, measuring, galvanized iron, as well as glass, ceramics, quartz, silicone resins, Phenolic resins and polytetrafluoroethylene »You can do them too use to make glass fabric and waterproofing materials from glass fabric, as well as various organic polymers in the form of shaped structures, for example foils, threads or coatings, to be glued together Examples of such polymers are polyimides, polyamic acids, polyamides, polybenzimidazoles, polybenthiazoles, polyoxydiaeols, polyphenylene ethers and polyesterο The metals can be surface treatments make necessary and in certain cases you can green « Use leftover information ^

Typical adhesive compositions are

(D

Yemetab & re Polyimide Precursors 125 Üropes

Aluminum dust 100 parts

Arsenic thioarsenate 20 Φβϋβ

Biraethylacetamide 188 ropes

■ cn) ■:.

Crosslinkable polyimide leader 125 3 parts

60 parts

21 -

0098 13/1786

763

Copper 8-quinolinolate 1 'part

Dimethylaeetamide 94 parts

Xylene 94 parts

(III)

Crosslinkable Polyimide Precursors 125 parts

Zinc dust 100 parts

Arsenic pentoxide 20 parts

Methylpyrollidon. 125 parts

Xylene 62 parts

These masses 60 Minutes "<prebaked ⁰ C 1'00 at-, then the? It is" bindimgsstelle with the introduced adhesive 120-30 minutes at 250 to 35O ⁰ C, preference. , 60 minutes at 300 ⁰ C 'hardened Druok, from touch to 25U 42.2 kg / cm, one can in -iiesem stage anwendem for optimum performance is then sin about 64 hours at 260 ⁰ O Uaehhärten wünschenswertο

If special properties are desired, the polyimides produced according to the invention can be coated with other poxy materials, for example with epoxy resins, silicone resins, phenolic resins: Polyvinylfonaäl =, aDev: al- or -butyral resins, with Polyurethanes, alkyd resins _f polyamide

22 -

009813/1796

FPO-1763

resins «polyester resins, nitrogen resins, for example melamine formaldehyde, urea formaldehyde, benzoguanamine formaldehyde and with polytetrafluoroethylene and copolymers _e

The invention is explained in more detail by the following examples » Unless otherwise stated, all details relate to weight

The production of some of the important components used in the examples is described below: The pyromellitic dianhydride used is obtained as white crystals _? by subliming the commercial product at 220 to 240 ⁰ C and a pressure of 0.25 to 1 mm Hg through silica gel «·

NfN-dimethylacetamide is produced by fractional distillation over phosphorus pentoxide; the fraction which ^{now distills at 73 0} G and 30 Hg is ϊί, Ν-Dimethylacetamidö

The viscosities of the diester diacid / diamine solvents given in the examples are determined with a Brockfield Vi8coaimeter *

. BAD ORlGlNAt.

009813/1796

FFD-1763

Example 1 . ,.

Production of the diethyl ester of 3.3 * .4.4'-benzophenone

tetraarboxylic acid

64 »4 parts 3,3 '» 4>4'-Be _! Nzophenon tetraoarbonic acid dianhydride is placed in a flask equipped with a stirrer and a reflux condenser o Then 257.6 parts of anhydrous ethanol (grade 2-B) are added and the mixture is stirred and heated under reflux. A sample of the solution obtained is tested in an ultrared = spectrophotometer · for absorption at 5.4 / ι and 5 * 6/1 »There is no such absorption, which means that there are no anhydride groups Excess ethanol by distillation at atmospheric pressure and finally in a water jet vacuum The product is a viscous, yellow-brown oil, which, as the following analysis shows, is the diethyl ester of 3,3 ', 4,4'-benzophenone tetracarboxylic acido analysis calculated for Cp ^ H -gOq. C 60.86 # H 4.35 % 0 34.78 # "■
Found? C 60.20 f H 4.43 1> 0 35.41 ^ o

24-.

009813/1796

Example 2 Preparation of the diethyl ester of pyromellitic acid

175 parts of pyromellitic dianhydride are placed in a flask equipped with a reflux condenser Product after taking it out; by keeping it overnight in a vacuum exsidcator. The pyromellitic acid dietary master bfei tiö to 164 ^ö Öo

Example 3

Preparation of the ester toiri precursors from 1 mole of 3.5 * ^ 4-4 "^ Bfeagptfcenöntfetragarbenp nsättreaianliydrid- and 1.5 mole of 4.4 * ~ ' methylene dianiline

128 «8 parts 3- ₉ 3 * _S! 4v4 ^l 'benzophenonetetracarboxylic dianhydride, 40y4 parts waeserfreies Ithanol and 207 »2 parts Dirnethylaeetemid adding to an TJmBetaungsgefäss equipped with a nitrogen" inlet tube, a stirrer and a heating mantle provided isto The mixture is stirred and the slurry heated under nitrogen to 1QO ⁰ O and receives at 100 ⁰ C. a clear 18-

²⁵ "009813/173 $ ^SA0

It

sung ο The iron 10O ⁰ Q temperature is maintained for 1 hour. Ahechliessend SiUhIt Maué the solution öüf 25 ⁰ O and add 118.8 parts 4I4 '~ Methylendiänilin under Kühren within 15 minutes hihzüo is then stirred the solution for a further 30 minutes to ensure mixing a -vollständiges "The solution has a Viseösität of 3 # 75 P (Eröckfield viscometer) and can be used as an insulating varnish or for other purposes specified below

When tested as insulating as in Example 4 (c) at 25 ⁰ C to give the following result set resin on spiral would take jje * »Ö # 51 g

Bond strength - 23 * 5 kg '+ ¹ »5 kg (90 Φ safety

border;
dohö 46.3 kg / g resin

Beiapie1 4 (a)

The procedure of Example 3 is repeated with the modification that 25 ₁ 78 parts of 3.3 ', 4.4' »benzophenone _{tetracarboxylic acid diethydride, 7?} 4 parts of anhydrous ethanol and 82.0 parts of N-methylpyrrolidone using ,, The slurry is heated to 6O ⁰ C and keeps DIE temperature at 60 + 3 ⁰ C 7 Stundeno Sine anaahliessend sample taken DIE * ser solution shows no absorption Ultrariot at 5.4 p. or 5; 6 U, indicating the absence of: a residual anhydride

0098 13/1796

FPIM 763

The solution is cooled to 25 ⁰ C and add 24.02 parts of 4,4 ^r -Oxydianilin within 5 minutes hinzuo The temperature is raised to 4O ⁰ C and holding for 30 minutes upright "The solution has a Vlscosität of A on the Gardner -Holt scale,

Example 4 (b>

Is poured from the solution of Examples 4 (a) both Glasais on aluminum panels using a O, 254 mm doctor blade Folieno The Flatten Burn 30 minutes at 15O ⁰ C and 5 minutes at 400 ⁰ C ₀ is obtained glöichmässige, golden brown , glossy, hard film coatings «>

Example 4 (c)

The usefulness of the solution according to 4 {a) as an adhesive and as an insulating varnish is shown below

Copper wire (1.024 mm), which is provided with a commercially available polyimide wire tuber, is placed on a 6.4 x mm mandrel in a helical snake shape. This snake is cut into 10.2 cm long spirals and annealed in a furnace 1 Stand at, 150 ⁰ C before = The spirals are then immersed in the after B-aj.e;. ::!. El 4 (a) prepared solution, keep it in it for 5 minutes, see s? .e langeam. vertical

27 "; ■ .-

00 98 13/1796 ^8AÖ

763

and läset out drain 20 Minuten "Then burns * it for 1 hour at 15O ⁰ Co Upon removal from the oven and cooling to ambient temperature, repeating the procedure, wherein one but the spirals in the opposite direction dipped pem second baking at 15O ⁰ C folgeein 16 hours final firing at 200 ⁰ C ₀ the by =-average recording of the converted resin (per coil) is O, J54 g ° the coils are then Bindungsfestig "strength after Dow Dexter tested in this test, the coils individually in a horizontal Position in a special clamping device in the jaws of a tensile tester of the Instron type.This keeps them in the form of a simple axis and exposes them to a knife edge until it breaks, which moves at a speed of 0.5 cm / min. moved <> The tensile stress ^J under which the spiral breaks is determined * The following results represent the average value of 10 determinations ο

Average binding strength (25 ⁰ C) - 26.94 kg f

0.82 kg (90 # safety limit)

Bond strength = it = 7S _f 4 kg / g resin

0098 13/1796

763

Example 5 (a)

Preparation of ffater ~ amine precursors from 1 mole 3 «3'.4» 4 '- ' benzophenone tetraarboxylic acid dianhydride and 1 «5 mole 4.4'-

Methylenedianillene

To a mixture of 82 parts of butyl alcohol and 85 ropes of H ^- methylpyrrolidone, which is in a flask with a reflux condenser? Stirrer, thermometer and heating mantle is provided, one adds 161 parts 3 »3 '» 4.4' ~ Benzophenontetracarbonsäiireeanhydrid ^{at 25 0 G o The reaction mixture is then heated to 10O 0} C and kept at this temperature for 30 minutes o Subsequently one adds to the reaction mixture 149 parts of 4 »4 * - = methylenedianiline and stir 50 Minuteno This is you aine mixture of 224 parts of xylene and 74 -T.eilen N-Methjlpyrrolidon added with stirring to provide a homogeneous solution to obtain ₀ The resulting varnish (X; contains 40 f "S'estatoffe, has a viscosity of 0.9 P and ÖIN Litergewiöht 1.08 iig

Helical test spirals made of wire ( 1.024 mm), the ml ·; m? olyimidla.3li: are predominant and 1 hour i3

2öÖ ° G temperi; v / urileüg taicht to 5 minutes in the shared by IeI 5 (a) hergef ι paint, can äiie 15 minutes from

2S · ". ■ -. ■■ .BAD

009813/1796

FPD-1763 30

dropwise and burns it for 1 hour at 15O ⁰ C ₀ then be reversed, the spirals and repeats the immersion, the drip "and the firing process. Mused Burn geprüfto the spirals then 4 hours at 225 ⁰ Co The Härzaufnähme is 0.42 g / Spiraleο These samples are on bonding strength as in Example 4 (c) in the various listed in the following table temperatures

commercially available paint (control) (k}

Check »
tempera
tur ⁰ C Aging time Weeks at 300 ⁰ C lacquer I
(kg) 25th no Weeks at 300 ⁰ C 15.01 180 no Weeks at 26O ⁰ C 9.34 25th 2 Weeks at 260 ^D C 8.71 25th 4th 3.67 25th 3 7.85 25th 6th 4.85 Example 5Cc)

4.63 3.22 1.77 1.63 2 ₉ 50 1.50

Twisted pairs ύοώ. 1.024 mm Brah! coated with polyimide, produced according to AIXE regulation Wr ₀ 57 and 1 hour tening at 20O ⁰ Cf, is thawed 5 minutes after the Iaok produced in Example 5 (a), allowed to drip off for 15 minutes and burn they 1 S'iuMe Lei 120 ⁰ C and 2 hours at 150 ⁰ Cn The twisted pairs are immersed again as described above, drained and burned and then 8 hours

30 =

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FFD-1763

at 225 ⁰ C burnt The samples are heat aged then at 260 C and 300 ⁰ C, and the time (hours) required until its breakdown strength to 100.0 toit gone down is to The results are eusanmiengefaest in the following table:

Time of going back (hours) Aging temperature varnish I Yergleiohaprobe with

commercial paint

Il

300 ⁰ C 1030 * 750

Example 5 (d)

Rings tear samples (Naval Ordinance Laboratory Rings) are prepared by saturating an IS-end glass silk strand (Type 801) with the lacquer prepared in Example 5 (a), shortly before placing it on a 12.7-cm mandrel under a voltage of 3.2 kg with U 4C / min, wound "the wet rings and the mandrel brerni to 2 hours at 15O ⁰ C and raises the temperature of 0 £ EN9 is within 5 hours at 37o C ⁰ the resin content of 7 # 0 The results of the strength test of the Rirge oind in de: c the following table summarized
Test tempera door R <ngi ;eremia 3feE > tip.ve i ·; (kg / cn)

24 ⁰ C • 5 027 ΐ2ΐ ° σ 5 giQ 26O ⁰ C 6th 749 316 ⁰ G 5 3C3

^51; 009813/1796

FFB-1763

The polymers fired in Examples 5 (a), 5 (C) ″ and 5 (d) are polyimides with the following repeating structural unit t

0 η

fl

in which the unsaturated bonds of nitrogen atoms with an arontitiechen? ef, o = carbon atom: Ln another equals: ftri üinheifc des Polymeris & us. composite «n sindo

0098 137 1796

Example 6 (a)

Production of a polyimide from 1 mol 3.3 '«4.4 ^> ° Benzo phenontetraoarboxylic acid dianhydride and 1.5 mol ^^'

dianiline

237.6 parts of ^ '- methylenedianiline, 669.6 parts of dimethylacetamide and 73.6 parts of anhydrous ethanol are added to a reaction vessel equipped with a stirrer, thermometer and a nitrogen inlet tube o The system is placed under nitrogen and 257.6 parts Parts of 3.3 '* 4.4-benzo'-phenontetracarboxylic acid dianhydride added with stirring'. The slurry is stirred and ^{heated to 65 0} O. This temperature is maintained for two hours? At the end of this time, the entire solid has gone into solution. The solution obtained has a viscosity of 36 P (Brockfield) *

Example 6 (b)

For use as an insulating varnish, the solution according to Example 6 (a) is reduced to a solids content of 32% with a mixture of 3 parts of xylene and 1 part of diine thjlacetamide. a viscosity of 4.75 P (Brookfield), and a Litergewrlcht of 1.03 feg / l ₀ films nan ana g of the above solution: leSBt _f. and in a Ziigprafvoriohtung the type In.stron jrlift, have the following. Own ». s uhaftent

■ : '■■■; .-. ORIGINAL BATHROOM

Sff

Stress at break 0.52 + 0.1 kg (ζ 10 *) Elongation at break »3» 1 + Ο # 9 Ji
Test conditions: temperature * 25 ⁰ C

Relative humidity «50 #

Speed of the crosshead " 0.5 om / min

Foil dioke (Duroheohnitt) - 0.0254 mn

The polymer is also tested as an insulating varnish: according to the in Example 4 (0) described expiry dates:

leaperatüj? ■ »18O ⁰ O

Har * Äufn * hae %% Spirmle »0.53 g

Bond strength = 22.14 + 0.68 kg

fii * this test one heats the snake dielectrically attf 180 ⁰ O ₆

Example 7

The procedure of Example 4 (a) is repeated using 25.78 parts of 3,5 ', 4 _i 4 ^f benzophenonetetracarboxylic dianhydride, 5.12 parts of absolute methanol and 82.0 parts Diaethylaoetamido HEATER The Ittfschlämmung * is ⁰ to 60 C and holding a temperature of 60 to 65 ⁰ C 3-1 / 2 hours upright Me solution is cooled to 28 ⁰ C and added over 5 minutes 24.02 parts of 4 _f 4 ^l -0xydianilin The hinzuo

.009813 / 1796

V- temperature is raised to 4O ⁰ C and holding for 30 minutes aufreoht to the solution of 4,4'-0xydianilin8 to fördernο you Viecosität the Ljösung is A-2 (Gardner Holt) and 1.15 P (Brookfleid) "

Example 8

104 parts of diethyl ester of 3 | 3 (prepared as described in Example 2) _'> 4.4 ^f -Benzophenontetraearboneäure one löet with agitation in a mixture of 59 parts Dimethylaoetarald and 119 parts of N-methyl pyrrolidone are added to this solution _o 74 * 25! Parts 4,4 '- !! ethylendianilino The mixture is stirred for 30 minutes to ensure a perfect solution

Example 9 Preparation of the ester-amine precursor from 1 mol of diethyl

eater of pyromellitic acid. 1 mole of 4,4'-diaminobenzophenone

and 0.5 moles of 4,4'-oxide / aniline

To 3 parts of 4.4 ^t -diaminobenzophenone, which is dissolved in 16 parts of dimethylacetamide, 3.5 parts of diethyl ester of pyromellitic acid, which was prepared as in Example 3, are added. After the solution has been stirred for two hours at ambient temperature, 1.4 parts are added. ^^ '- Oxydianiline and 4 parts of diethyl acetamide added.

3i5 -

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den and adds 28 parts of N-methylpyrrolidone to the To reduce viscosity to a viscosity suitable for film casting ο

Ists is poured a film on a glass plate using a 0.178 mm-Eakel and burns for 15 minutes at 15O ⁰ C and 3 minutes at 40O ⁰ Co The baked film consists of a polyimide, which characterized by the following recurring structural unit

(t

C «

■ 0

. Il

ti

Il

Il

0 0 9 8 13/179 6

3V

in which the dangling bonds dee stickst offadorns are connected with an aromatic Ketoatom in a same unit of the polymer _o

The mixture is poured onto a glass plate using a doctor blade foils and burns for 30 minutes at 150 ⁰ O, and 16 hours at 200 ⁰ Co The films removed from the plate and checks them in the tensile tester of the type Instron as in Example 6 (b) described

Stress at break «0.45 + 0.056 kg / cm (ac ΙΟ" ') Elongation at break -3 * 0 + $ 0.4

Example 10

The procedure of Example 3 is repeated, but using 126 parts of methylenedioyclohsxylarain instead of 118.8 parts of 4 _? 4 * -Öxydianilin that wurdt used in Example 3. * = M n obtained a crystalline precipitate, which NaOH is allowed to stand overnight at ambient temperature in solution and forms a clear solution, the SSMA Sinsata as Isolierl & ck vie by coating and firing the spirals in Example 4 (o) is suitable *

The procedure similar to Example 8 is modified with the modification

009813/11 ^ 8

PFIM 763 3?

repeats that 47.3 parts of nonaraethylenediamine are used instead of 74.25 parts of 4,4 * -methylene dianiline? A crystalline precipitate is obtained which, after standing, goes into solution to form a clear solution which is suitable for use as an adhesive by application to a substrate and baking as in Example 9

Example 12

10 strips of stainless steel (10 cm χ χ 2.5 cm 0.13 cm; 17 "7HI, condition A) was degreased with Trichloräthylendampf, dried, they immersed for 10 minutes in an alkaline petitioner Gent solution at 75 ⁰ C, it flushes with water and dried in a forced air oven at 93 ⁰ Co is subsequently etched up to a line extending 2.5 cm from one end removed is by placing them for 10 minutes in a sulfuric acid solution at 68 ⁰ O and then for 10 minutes ir. a hydrofluoric-nitric acid solution was immersed in fiaumtemperatur is then rinsed in distilled water and dried in an air oven at 93 ⁰ Co

The etched ends by coating on one side with the * according to Example 6 (a) prepared solution by being anstreichtο with a camel hair brush, the coated strip is dried 30 minutes at 100 G ^0, sets two strips so

009813/1796

WD-1763

one on top of the other so that they overlap one another by 1.3 and cured in a press for 1 hour at 30O ⁰ C and a pressure of 14.1 kg / om _β Aiteehliessend they are cured for 64 hours at 260 ⁰ O.

The adhesive bonds are checked by shear effects in a tester of the Instron type at 1.3 mm / lead, whereby the following results are obtained «

At 25 ° C / 112.5 kg / om ² , 100.1 kg / cm ²

° at 300 C / 77.9 kg / om ^2, 75 x 1 kg / cm ²

at 371 ⁰ C / 68.6 kg / om ²

Example 13

The procedure of Example 3 is repeated with the modification that instead of 118.8 parts, 95.1 parts of 4.4 ^{liters of} methylenedianiline are used. The solution obtained is suitable for use as an insulating varnish by coating and baking as in Example 4 (c) _O

Example 14

The procedure of Example-5 (a) is repeated with the Modification to use 199 parts of 4,4'-methylenedianiline instead of 149 parts.

- 39 -

009813/1796

FFD-1763

Suitable for all insulating varnishes. Helical spirals, produced and tested as in Example 5 (b), show a bond strength (25 ⁰ O) of 12.02 kg

• 40

0098 13/1796

Claims (1)

Pat e η t a n a ρ r tt ehe 1 «Intimate mixture of a diamine and a diester an organic tetracarboxylic acid with the formulas respectively ' > COOH where R _{12 is} alkyl or aralkyl, the arrow is isomerism, K is an organic divalent radical and A is a tetravalent organic radical with two Oarbonylgruppepaaren (-C-) means »where the Oarbonyl« P. groups of each pair (-C-) to neighboring carbon- » atoms are bonded in A, and where at least one of the radicals A or M contains an aromatic keto group and in an amount of at least 30 mol #, based on the existing beasts »and the diamine in one at least 15 molar excess, based on the diester, was present ο mass according to claim 1 in the form of a solution »where A is a represents an aromatic radical - 41 - 009813/1796 FFB-1763 Composition according to claim 2, characterized in that the biamine is hexamethylenediamine, methylenedianiline, oxydianiline or biaminofcenzophenone and the biester is a beast of benzophenonetraearboxylic acid, methylenediphthalic acid, oxydiphthalic acid or pyromellitic acid » 4ο solution according to claim 2, characterized in that the Beast is a beast of benzophenone tetracarboxylic acid 5ο solution according to claim 2, characterized in that the Beast is a beast of pyromellitic acid 6 »Solution according to claim 2, characterized in that the Beast is a beast of oxydiphthalic acid ο 7ο solution according to claim 2, characterized in that, the Biamin methylenedianiline isto 8ο solution according to claim 2, characterized in that the Biamin 4,4'-Biaminobenzophenon isto 9ο solution according to claim 2, characterized in that the Biamin Oxydianiline isto 10. Solution according to claim 2, characterized in that the Biamin hexamethylenediamine is ~ - 42 - 009813/1796 PPD-I763 11o polymer, identified by the recurring Structural units AA ⁵ W. η O \ ψ \ γ where χ and y according to 2β represent numbers which represent the number of units in brackets »the carbonyl pairs 1,2, 3,4, 5» 6, 7 »8, 9,10,11,12, 13,14 and 15,16 adjacent carbon atoms are bonded in the respective beds R ^ *, and in which at least 20 # of the radicals R | _n> _{contain a nucleus-end group CbN-R 0} -K =, in which the carbon atom connects an aromatic ring directly with another carbon atom, and wherein the niohi unsaturated bonds of the nitrogen atom are connected to an adjacent unit of the Polymeriaatee, resulting in a crosslinked polymeric structure, and wherein each of the radicals R _{1-8 is} an aliphatic aromatic, carbocycliBiher '.. or heterocyclic radical ο - 43 - BAD ORIGINAL ' 0098 13/1796 FFD «1763 12o- polymer with the structural formula according to claim 11, characterized in that the remainder Rg is an organi scher best is with the formula n H N η is, in which B _{8 represents} alkylene or arylene » 13 ° polymer with the structural formula according to claim 11, characterized in that Be is a hydrogen hydrogen rest ait of the formula % \ jr —CH «- is < Polymer with the structural formula according to claim 11 # characterized in that R ~ is an organic residue with the formula ►- 0 - - 44 - 009813/1796 FED-1763- ':. ¹ ct ^ oljrmeriaat with the structural formula according to claim 11, characterized in that Hc is an organic residue with the formula ". ■. ^: - ■ ■■ ■ H. '- is where Eg represents alkylene or arylene. " o. Adhesive mass j consisting essentially of a Ge raisch after Mspruoh 1 ο 17 * adhesive mass, "beetehenö essentially from the solution according to claim Za 18o adhesive massea consisting essentially of the solution according to claim 3 ο 19o laminate with an adhesive layer consisting essentially of the polymer according to the claim. 11 * '[' * -. ■■■ -. ■: ■■■. , - ^: '..' · ■ = '^ äöa folie bestshend from the Folymeriaat after Anöpruoh 11 _{Q 4t} . BATH ORIGINAL 009813/1796 21o process for the production of a polyimide, characterized * that a diamine with the formula HgN = M-NHg is reacted with a diester of a tetracarboxylic acid, which the formula ^ COO-R ₁₂ ^ ⁵ TIOOH where the heat R ^ _{2 is} alkyl or aralkyl, A is a tetravalent organic bed with 2 carbonylgiruppenpaaren (-CU) "to which the carbonyl groups of each pair are bonded in such a way that they are located on adjacent carbon atoms in A, where at least one of the best A or M contains an aromatic keto group and is present in an amount of 30 mol, based on the beast present, and the diamine in an at least 15 mol-S ^ igen overseas, including "the diester, present; the reaction being carried out at an elevated temperature until essentially all of the diamine has reacted » 009813/1796